CN107021876B - CCUS system and process method applied to petroleum and petrochemical industry - Google Patents
CCUS system and process method applied to petroleum and petrochemical industry Download PDFInfo
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- CN107021876B CN107021876B CN201710371919.5A CN201710371919A CN107021876B CN 107021876 B CN107021876 B CN 107021876B CN 201710371919 A CN201710371919 A CN 201710371919A CN 107021876 B CN107021876 B CN 107021876B
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000003208 petroleum Substances 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 219
- 239000007789 gas Substances 0.000 claims abstract description 125
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003546 flue gas Substances 0.000 claims abstract description 25
- 238000002407 reforming Methods 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 239000003345 natural gas Substances 0.000 claims abstract description 15
- 238000006057 reforming reaction Methods 0.000 claims abstract description 12
- 238000002485 combustion reaction Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 103
- 238000010521 absorption reaction Methods 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 29
- 238000006073 displacement reaction Methods 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 238000006297 dehydration reaction Methods 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 13
- 239000000446 fuel Substances 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000004391 petroleum recovery Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- 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
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- 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
-
- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B33/00—Steam-generation plants, e.g. comprising steam boilers of different types in mutual association
- F22B33/18—Combinations of steam boilers with other apparatus
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
- F23L7/00—Supplying non-combustible liquids or gases, other than air, to the fire, e.g. oxygen, steam
- F23L7/007—Supplying oxygen or oxygen-enriched air
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/32—Direct CO2 mitigation
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
-
- 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
- Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
- Y02P90/70—Combining sequestration of CO2 and exploitation of hydrocarbons by injecting CO2 or carbonated water in oil wells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Fluid Mechanics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a CCUS system and a process method applied to petroleum and petrochemical industry, wherein the CCUS system separates air to obtain nitrogen and oxygen-enriched air, the oxygen-enriched air is introduced into a gas steam boiler to be mixed and combusted with fuel natural gas, one part of obtained flue gas is used as circulating gas to be mixed with the oxygen-enriched air to enter the boiler, the other part of the flue gas and the fuel natural gas are subjected to triple reforming reaction in a triple reforming reactor, and two utilization modes are adopted for synthesis gas obtained by the reaction: one is directly reinjecting oil reservoir to drive oil, the other is synthesizing DME in one step by entering slurry bed reactor, condensing by condenser, obtaining CO step by separating device, absorbing device and rectifying device 2 DME, methanol and water, and N obtained by an air separation apparatus 2 Gas-fired steam boilerGenerated steam, CO 2 CO separated by the separating device 2 And simultaneously injecting into oil reservoir to drive oil. The invention combines the oxygen-enriched combustion technology, the natural gas and flue gas three-reforming technology and the one-step synthesis DME technology to obtain various gases and DME, methanol and water for recycling.
Description
Technical Field
The invention relates to the technical field of oil field resource utilization, in particular to a CCUS system and a process method applied to the petroleum and petrochemical industry.
Background
Global warming causes the problems of rising average surface temperature, extreme climate occurrence, seawater acidification and the like to become important problems of attention in the world today, and the survival and development of human beings are seriously affected. The root cause of global warming is the greenhouse gas CO 2 Thereby reducing CO 2 Emissions are critical to alleviating climate warming.
In recent years, CCS (Carbon Capture and Storage) is a focus of attention of international society, while China is a developing country, and is increasingly developing economy, and in combination with the reality of the country, a CCUS (Carbon Capture, utilization and Storage) is proposed on the basis of CCS, namely capturing, utilizing and sealing Carbon dioxide. The CCUS technology is an emerging leading edge technology and plays a vital role in controlling carbon dioxide emission and realizing sustainable development. China faces the serious problem of high carbonization of an energy structure, and the situation is not optimistic, the share of carbon emission in the petroleum and petrochemical industry is quite large, and the pressure and the constraint of coping with climate change are increasing. But from the development characteristics of the industry, further worsening of the problem of alleviation is called daily.
The CCUS technology involves a plurality of technical links such as capturing, transporting, sealing and utilizing carbon dioxide, and the high cost of the technology is an important factor for restricting the development of the whole industrial chain. Generally, for the petroleum and petrochemical industry, in order to meet the requirements of petroleum development and improve the petroleum recovery rate, carbon dioxide is generally injected into oil reservoirs for displacement of oil, and the gas source is mostly CO in flue gas from coal-fired power plants 2 While the main component in the flue gas is nitrogen, the content of carbon dioxide is relatively low, thereby leading to high separation energy consumption,the trapping cost is high; captured CO 2 And transported to the corresponding oil well through the pipeline, which in turn increases the cost of higher pipeline laying. Therefore, how to reasonably utilize the resources in the whole process and utilize the obtained product as resources is realized, so that a polygeneration energy system with higher flexibility is constructed, and the polygeneration energy system is a shortcut for fundamentally improving the economy.
Disclosure of Invention
The invention aims to overcome the defects of the background technology, provide a CCUS system applied to the petroleum and petrochemical industry, fully surround the flue gas generated by a gas steam boiler in an oil field, combine an oxygen-enriched combustion technology, a natural gas and flue gas three-reforming technology and a one-step synthesis DME (dimethyl ether) technology, and recycle various gases and fuel-grade DME, methanol and water, and provide a technological method of the system.
In order to achieve the aim, the CCUS system applied to the petroleum and petrochemical industry comprises an air separation device, a gas steam boiler, a triple reforming reactor, a heat exchanger, a slurry bed reactor, a condenser, a gas-liquid separator, an absorption tower, a pressure swing adsorption device, a methanol dehydration reactor, a DME rectifying tower and CO 2 A separator, a methanol rectifying column;
the air separation device is provided with a nitrogen outlet for reinjection of an oil reservoir for oil displacement, the oxygen-enriched outlet of the air separation device is connected with the oxygen-enriched inlet of the gas steam boiler through a first pipeline, the first flue gas outlet of the gas steam boiler is connected with the first pipeline, the second flue gas outlet of the gas steam boiler is connected with the flue gas inlet of the triple reforming reactor, the gas steam boiler is further provided with a natural gas inlet and a steam outlet for reinjection of the oil reservoir for oil displacement, the steam outlet of the gas steam boiler is connected with the steam inlet of the triple reforming reactor through a branch, and the gas outlet of the gas steam boiler is connected with the gas inlet of the triple reforming reactor;
the synthesis gas outlet of the triple reforming reactor is connected with the synthesis gas inlet of the heat exchanger through a second pipeline, the high-temperature synthesis gas outlet of the heat exchanger is connected with the high-temperature synthesis gas inlet of the slurry bed reactor, the reaction product outlet of the slurry bed reactor is connected with the reaction product inlet of the heat exchanger, the low-temperature reaction product outlet of the heat exchanger is connected with the low-temperature reaction product inlet of the condenser, the gas-liquid mixture outlet of the condenser is connected with the gas-liquid mixture inlet of the gas-liquid separator, the gas-phase outlet of the gas-liquid separator is connected with the gas-phase inlet of the absorption tower, and the liquid-phase outlet of the gas-liquid separator is connected with the first inlet of the DME rectifying tower;
the absorption liquid outlet of the absorption tower is connected with the absorption liquid inlet of the methanol dehydration reactor, the product outlet of the methanol dehydration reactor is connected with the second inlet of the DME rectifying tower, the DME rectifying tower is also provided with a DME outlet, the crude methanol solution outlet of the DME rectifying tower is connected with the crude methanol solution inlet of the methanol rectifying tower, the methanol outlet of the methanol rectifying tower is connected with the methanol inlet of the absorption tower, and the water outlet of the methanol rectifying tower is connected with the water inlet of the gas steam boiler.
In the above technical scheme, the pressure swing adsorption device is further comprised, a top gas outlet of the absorption tower is connected with a gas inlet of the pressure swing adsorption device, and a gas outlet of the pressure swing adsorption device is connected with a second pipeline.
In the technical proposal, it also comprises CO 2 Separator, mixed gas outlet of DME rectifying tower and CO 2 The mixed gas inlet of the separator is connected, and the CO 2 The separator is also provided with CO for reinjection of oil reservoirs for oil displacement 2 And an outlet.
In the above technical solution, the CO 2 The separator is a membrane separator.
In the technical scheme, a pump is arranged on a pipeline between the water outlet of the methanol rectifying tower and the water inlet of the gas steam boiler.
In the above technical scheme, the absorbent of the absorption tower is methanol.
In the technical scheme, the reaction temperature of the slurry bed reactor is 260-270 ℃ and the reaction pressure is 3-5MPa.
In the technical scheme, the temperature of the top of the DME rectifying tower is 20-90 ℃, the temperature of the bottom of the DME rectifying tower is 150-220 ℃, and the pressure is 0.2-2.2MPa.
In the technical scheme, the temperature of the top of the methanol rectifying tower is 40-90 ℃, the temperature of the bottom of the methanol rectifying tower is 80-150 ℃, and the pressure is 0.1-0.8MPa.
The invention also provides a process method of the CCUS system applied to the petroleum and petrochemical industry, which comprises the following steps:
1) The air is separated by an air separation device to obtain nitrogen and oxygen-enriched air, the nitrogen is directly reinjected into an oil reservoir to drive oil, and the oxygen-enriched air is introduced into a gas steam boiler to be mixed with natural gas for combustion to obtain steam and flue gas; one part of the steam is injected into an oil reservoir to drive oil, and the other part of the steam is used as supplementary steam for triple reforming reaction; part of the flue gas and the oxygen-enriched gas are mixed and enter a gas steam boiler for recycling, and the other part of the flue gas enters a triple reforming reactor to perform triple reforming reaction with natural gas, oxygen and steam to generate synthesis gas;
2) One part of the synthesis gas obtained by the triple reforming reactor is directly reinjected into an oil reservoir for oil displacement, and the other part of the synthesis gas is subjected to heat exchange with a reaction product obtained after the reaction of the slurry bed reactor by a heat exchanger and then enters the slurry bed reactor for reaction, wherein the reaction temperature in the slurry bed reactor is 260-270 ℃, and the reaction pressure is 3-5MPa;
4) The reaction product of the slurry bed reactor enters a condenser to be condensed to 30-40 ℃ after heat exchange of a heat exchanger, wherein methanol steam and DME steam are condensed into liquid phase products, and noncondensable gases CO and CO are obtained 2 、H 2 And the uncondensed DME gas is used as a gas phase product, the liquid phase product and the gas phase product enter a gas-liquid separator for separation, and the gas phase product enters an absorption tower for absorption by methanol and then is non-condensable gases CO and H 2 Discharging from the top of the absorption tower, recycling the synthetic raw materials through the pressure swing adsorption device, and circulating the synthetic raw materials into a second pipeline;
5) The absorption liquid at the bottom of the absorption tower enters a methanol dehydration reactor to react to obtain the catalyst containing dimethyl ether, water and CO 2 The product and the liquid phase product of the gas-liquid separator enter a DME rectifying tower together, rectifying and separating are carried out under the pressure of 0.2-2.2MPa, the temperature of the tower top is 20-90 ℃, the temperature of the tower bottom is 150-220 ℃,distilling off DME;
6) The mixed gas obtained by the DME rectifying tower enters CO 2 Separator, separated CO 2 Injecting oil reservoir oil displacement; the crude methanol solution obtained by the DME rectifying tower enters the methanol rectifying tower, rectifying and separating are carried out under the pressure of 0.1-0.8MPa, methanol and water are separated, the methanol returns to the absorption tower, and the water is pumped into a gas steam boiler for recycling.
Compared with the prior art, the invention has the following advantages:
firstly, the invention introduces the oxygen-enriched combustion technology into the gas steam boiler in the oil field, in the process, because the air does not contain N 2 The participation of NOx is reduced, so that the pollutant emission is cooperatively controlled, and the atmospheric environment is protected; simultaneously, a large amount of oxygen participates in the combustion of the fuel more fully, the combustion efficiency of the boiler is improved, and the generated CO is also caused 2 Higher concentration provides sufficient reactant (CO) for the subsequent triple reforming reaction 2 、O 2 ) Thereby synthesizing more fuel DME. The fuel DME has good combustion performance, high heat efficiency, no residual night and no black smoke in the combustion process, is a high-quality and clean fuel, does not harm an ozone layer, effectively protects the environment, and has the resource profile of oil deficiency and gas deficiency in China, so the fuel DME is hopeful to become a main petroleum substitute product.
Secondly, the invention can separate N obtained by the air separation device 2 Steam and CO generated by gas steam boiler 2 CO separated by the separating device 2 Simultaneously, the oil reservoir is injected for oil displacement, so that the oil field recovery ratio is improved, the dual benefits of environment and economy are realized, the obtained methanol is used as an absorbent, the inside is recycled, the obtained water is used as boiler water supply, steam is generated by pumping the boiler, and the oil reservoir can be well recycled, so that considerable economic benefits are generated.
Thirdly, the invention realizes the purposes of improving the DME conversion rate and saving energy and reducing consumption in the separation process of synthesizing DME by a one-step method, and the heat exchanger is arranged to exchange heat between the raw material synthetic gas and the reacted gas product, so that the raw material synthetic gas is raised to the temperature (270 ℃) participating in the reaction, and the temperature of the reacted gas product is reduced, thereby reducing the consumption of cold energy for the subsequent process. The added methanol dehydration reactor, the reactant comes from the absorbent methanol, so that the conversion rate of DME is greatly improved.
Fourth, the resources in the whole system of the invention can be obtained and utilized on site, the pipeline laying cost, the long-distance transportation cost and the noncondensable gas recovery cost are saved, the fuel natural gas required by the gas-fired steam boiler can be directly obtained from an oil field, and the raw material CH required by the triple reforming reaction is obtained 4 、CO 2 、H 2 O、O 2 Sufficient, can be obtained directly in the hearth and adopts O 2 /CO 2 Combustion technology, saving high CO 2 The trapping cost is high, and the noncondensable gas coming out from the top of the absorption tower is used for recovering useful component H through pressure swing adsorption 2 And (3) recycling CO serving as a raw material of the synthesis gas.
Fifth, the invention has very good prospect in the petroleum and petrochemical industry, the carbon dioxide oil displacement has obvious effect on improving the recovery ratio of the ultra/ultra low permeability oil field, and through geological evaluation, about 100 hundred million tons of petroleum geological reserves in China are suitable for adopting carbon dioxide oil displacement. According to the total implementation of carbon dioxide oil displacement measurement and calculation, the recoverable reserves can be expected to be increased by 7 hundred million tons to 14 hundred million tons. In addition, the produced product DME can replace liquefied petroleum gas, and temporarily relieves the situation of insufficient petroleum supply.
Drawings
FIG. 1 is a schematic diagram of a CCUS system for use in the petrochemical industry;
Detailed Description
The following describes the embodiments of the present invention in detail with reference to examples, but they are not to be construed as limiting the invention. While at the same time becoming clearer and more readily understood by way of illustration of the advantages of the present invention.
As shown in the figure, the CCUS system applied to the petroleum and petrochemical industry comprises an air separation device 1, a gas steam boiler 2, a triple reforming reactor 3, a heat exchanger 4, a slurry bed reactor 5, a condenser 6, a gas-liquid separator 7, an absorption tower 8, a methanol dehydration reactor 10, a DME rectifying tower 11 and a methanol rectifying tower 13;
the air separation device 1 is provided with a nitrogen outlet 1.1 for oil displacement of a reinjection oil reservoir, an oxygen-enriched outlet 1.2 of the air separation device 1 is connected with an oxygen-enriched inlet 2.1 of the gas steam boiler 2 through a first pipeline 15.1, a first flue gas outlet 2.2 of the gas steam boiler 2 is connected with the first pipeline 15.1, a second flue gas outlet 2.3 of the gas steam boiler 2 is connected with a flue gas inlet 3.1 of the triple reforming reactor 3, the gas steam boiler 2 is also provided with a natural gas inlet 2.4 and a steam outlet 2.5 for oil displacement of the reinjection oil reservoir, the steam outlet 2.5 of the gas steam boiler 2 is connected with a steam inlet 3.2 of the triple reforming reactor 3 through a branch, and the gas outlet 2.6 of the gas steam boiler 2 is connected with the gas inlet 3.3 of the triple reforming reactor 3;
the synthesis gas outlet 3.4 of the three reforming reactor 3 is connected with the synthesis gas inlet 4.1 of the heat exchanger 4 through a second pipeline 15.2, the high-temperature synthesis gas outlet 4.2 of the heat exchanger 4 is connected with the high-temperature synthesis gas inlet 5.1 of the slurry bed reactor 5, the reaction product outlet 5.2 of the slurry bed reactor 5 is connected with the reaction product inlet 4.3 of the heat exchanger 4, the low-temperature reaction product outlet 4.4 of the heat exchanger 4 is connected with the low-temperature reaction product inlet 6.1 of the condenser 6, the gas-liquid mixture outlet 6.2 of the condenser 6 is connected with the gas-liquid mixture inlet 7.1 of the gas-liquid separator 7, the gas-phase outlet 7.2 of the gas-liquid separator 7 is connected with the gas-phase inlet 8.1 of the absorber column 8, and the liquid-phase outlet 7.3 of the gas-liquid separator 7 is connected with the first inlet 11.1 of the DME rectifying column 11;
the absorbent of the absorption tower 8 is methanol, an absorption liquid outlet 8.2 of the absorption tower 8 is connected with an absorption liquid inlet 10.1 of a methanol dehydration reactor 10, a product outlet 10.2 of the methanol dehydration reactor 10 is connected with a second inlet 11.2 of a DME rectifying tower 11, the DME rectifying tower 11 is also provided with a DME outlet 11.3, a crude methanol solution outlet 11.4 of the DME rectifying tower 11 is connected with a crude methanol solution inlet 13.1 of a methanol rectifying tower 13, a methanol outlet 13.2 of the methanol rectifying tower 13 is connected with a methanol inlet 8.4 of the absorption tower 8, a water outlet 13.3 of the methanol rectifying tower 13 is connected with a water inlet 2.7 of a gas steam boiler 2, and a water outlet 13.3 of the methanol rectifying tower 13 is connected with the gas steam boiler 2A pump 14 is arranged in the line between the water inlets 2.7. The top gas outlet 8.3 of the absorption tower 8 is connected with the gas inlet 9.1 of the pressure swing adsorption device 9, and the gas outlet 9.2 of the pressure swing adsorption device 9 is connected with the second pipeline 15.2. Mixed gas outlet 11.5 of DME rectifying tower 11 and CO 2 The mixed gas inlet 12.1 of the separator 12 is connected, said CO 2 Separator 12 is also provided with CO for reinjection of reservoirs for displacement of reservoir oil 2 Outlet 12.2. The CO 2 Separator 12 is a thin film separator.
The invention relates to a process method of a CCUS system applied to petroleum and petrochemical industry, which comprises the following steps:
1) Air is separated by an air separation device 1 to obtain nitrogen and oxygen-enriched air, the nitrogen is directly reinjected into an oil reservoir to drive oil, and the oxygen-enriched air is introduced into a gas steam boiler 2 to be mixed with natural gas for combustion to obtain steam and flue gas (containing 65 mass percent of CO) 2 H with mass percent of 30% 2 O); one part of the steam is injected into an oil reservoir to drive oil, and the other part of the steam is used as supplementary steam for triple reforming reaction; part of the flue gas and the oxygen-enriched gas are mixed and enter the gas steam boiler 2 for recycling, another part of the gas enters a triple reforming reactor 3 to carry out triple reforming reaction with natural gas, oxygen and steam to generate synthesis gas (H) 2 、CO、H 2 O); among them, the triple reforming reaction mainly has four reactions: the carbon dioxide reforming reaction of methane, the steam reforming reaction of methane, the partial oxidation reaction of methane and the complete oxidation reaction of methane, wherein the first two reactions are strong endothermic reactions, the second two reactions are strong exothermic reactions, when the four reactions are carried out simultaneously, the defect of high endothermic heat of the reforming reaction is overcome, the reaction is in a 'thermal neutral' state, the energy loss is greatly reduced, and the reaction formula is as follows:
CH 4 +CO 2 ＝2CO+2H 2 (ΔH 0 ＝247.3kJ/mol)
CH 4 +H 2 O＝CO+3H 2 (ΔH 0 ＝206.3kJ/mol)
CH 4 +1/2O 2 ＝CO+2H 2 (ΔH 0 ＝-35.6kJ/mol)
CH 4 +2O 2 ＝CO 2 +2H 2 O(ΔH 0 ＝-880kJ/mol)
the triple reforming reactor is arranged at the hearth outlet of the gas steam boiler, and fully utilizes the high temperature condition of the hearth outlet of about 1000 ℃ and on-site raw materials (natural gas, oxygen and flue gas).
2) One part of the synthesis gas obtained by the triple reforming reactor 3 is directly reinjected into an oil reservoir for oil displacement, and the other part of the synthesis gas is subjected to heat exchange with a reaction product obtained by reacting with the slurry bed reactor 5 through a heat exchanger 4 and then enters the slurry bed reactor 5 for one-step synthesis DME reaction, wherein the reaction temperature in the slurry bed reactor 5 is 260-270 ℃, and the reaction pressure is 3-5MPa; wherein, the one-step synthesis of DME means that the synthesis gas completes the methanol synthesis and the methanol dehydration reaction simultaneously in a slurry bed reactor. The methanol synthesized in the reaction can be dehydrated quickly to generate DME, and the dehydrated H2O is consumed by CO, so that the chemical balance limit of the methanol synthesis reaction is broken. Due to the combined action of these reactions, a strong synergistic effect is produced, greatly increasing the conversion of synthesis gas. The reaction formula is:
CO+2H 2 →CH 3 OH+90.4kJ
2CH 3 OH→CH 3 OCH 3 +H 2 0+23.4kJ
CO+H 2 O→H 2 +CO 2 +40.9kJ
3) The reaction product of the slurry bed reactor 5 enters a condenser 6 to be condensed to 30-40 ℃ after heat exchange of a heat exchanger 4, wherein methanol steam and DME steam are condensed into liquid phase products, and noncondensable gases CO and CO 2 、H 2 And uncondensed DME gas is used as a gas phase product, the liquid phase product and the gas phase product enter a gas-liquid separator 7 for separation, and the gas phase product enters an absorption tower 8 for absorption by methanol and then is non-condensable gases CO and H 2 The synthetic raw materials are discharged from the top of the absorption tower 8 and recycled to enter a second pipeline 15.2 through the pressure swing adsorption device 9;
4) The absorption liquid at the bottom of the absorption tower 8 enters a methanol dehydration reactor 10 to react to obtain the liquid containing dimethyl ether, water and CO 2 The product and the liquid phase product of the gas-liquid separator 7 are fed into a DME rectifying tower 11 together and are carried out under the pressure of 0.2-2.2MPaRectifying and separating, wherein the temperature of the top of the tower is 20-90 ℃, the temperature of the bottom of the tower is 150-220 ℃, and rectifying DME;
5) The mixed gas obtained by the DME rectifying tower 11 enters CO 2 Separator 12, separated CO 2 Injecting oil reservoir oil displacement; the crude methanol solution obtained by the DME rectifying tower 11 enters a methanol rectifying tower 13, and is subjected to rectifying separation under the pressure of 0.1-0.8MPa, methanol and water are separated, the methanol returns to the absorption tower 8, and the water is sent into the gas steam boiler 2 by a pump 14 for recycling. N obtained by separating steam generated by a boiler from air 2 、CO 2 CO separated by the separating device 2 Simultaneously injecting oil reservoir oil displacement, realizing 'one furnace three injection'.
The foregoing is merely exemplary embodiments of the present invention, and it should be noted that any changes and substitutions that would be easily recognized by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (5)
1. Be applied to CCUS system of petrochemical industry, its characterized in that: comprises an air separation device (1), a gas steam boiler (2), a triple reforming reactor (3), a heat exchanger (4), a slurry bed reactor (5), a condenser (6), a gas-liquid separator (7), an absorption tower (8), a methanol dehydration reactor (10), a DME rectifying tower (11) and a methanol rectifying tower (13);
the air separation device (1) is provided with a nitrogen outlet (1.1) for reinjection of oil reservoirs for oil displacement, an oxygen-enriched outlet (1.2) of the air separation device (1) is connected with an oxygen-enriched inlet (2.1) of a gas steam boiler (2) through a first pipeline (15.1), a first flue gas outlet (2.2) of the gas steam boiler (2) is connected with the first pipeline (15.1), a second flue gas outlet (2.3) of the gas steam boiler (2) is connected with a flue gas inlet (3.1) of a triple reforming reactor (3), the gas steam boiler (2) is further provided with a natural gas inlet (2.4) and a steam outlet (2.5) for reinjection of oil reservoirs for oil displacement, the steam outlet (2.5) of the gas steam boiler (2) is connected with the steam inlet (3.2) of the triple reforming reactor (3) through a branch, and a gas outlet (2.6) of the gas steam boiler (2) is connected with the gas inlet (3.3) of the triple reforming reactor (3);
the synthesis gas outlet (3.4) of the three reforming reactor (3) is connected with the synthesis gas inlet (4.1) of the heat exchanger (4) through a second pipeline (15.2), the high-temperature synthesis gas outlet (4.2) of the heat exchanger (4) is connected with the high-temperature synthesis gas inlet (5.1) of the slurry bed reactor (5), the reaction product outlet (5.2) of the slurry bed reactor (5) is connected with the reaction product inlet (4.3) of the heat exchanger (4), the low-temperature reaction product outlet (4.4) of the heat exchanger (4) is connected with the low-temperature reaction product inlet (6.1) of the condenser (6), the gas-liquid mixture outlet (6.2) of the condenser (6) is connected with the gas-liquid mixture inlet (7.1) of the gas-liquid separator (7), the gas outlet (7.2) of the gas-liquid separator (7) is connected with the gas inlet (8.1) of the absorber (8), and the gas-liquid mixture outlet (7.3) of the gas-liquid separator (7) is connected with the first distillation column (11.11);
an absorption liquid outlet (8.2) of the absorption tower (8) is connected with an absorption liquid inlet (10.1) of a methanol dehydration reactor (10), a product outlet (10.2) of the methanol dehydration reactor (10) is connected with a second inlet (11.2) of a DME rectifying tower (11), the DME rectifying tower (11) is also provided with a DME outlet (11.3), a crude methanol solution outlet (11.4) of the DME rectifying tower (11) is connected with a crude methanol solution inlet (13.1) of a methanol rectifying tower (13), a methanol outlet (13.2) of the methanol rectifying tower (13) is connected with a methanol inlet (8.4) of the absorption tower (8), and a water outlet (13.3) of the methanol rectifying tower (13) is connected with a water inlet (2.7) of a gas steam boiler (2);
the device also comprises a pressure swing adsorption device (9), wherein a top gas outlet (8.3) of the absorption tower (8) is connected with a gas inlet (9.1) of the pressure swing adsorption device (9), and a gas outlet (9.2) of the pressure swing adsorption device (9) is connected with a second pipeline (15.2);
it also comprises CO 2 A separator (12) for mixing the mixed gas outlet (11.5) of the DME rectifying tower (11) with CO 2 The mixed gas inlet (12.1) of the separator (12) is connected, and the CO 2 The separator (12) is also provided with CO for reinjecting the oil reservoir to drive oil 2 An outlet (12.2);
the reaction temperature of the slurry bed reactor (5) is 260-270 ℃ and the reaction pressure is 3-5MPa;
the temperature of the top of the DME rectifying tower (11) is 20-90 ℃, the temperature of the bottom of the DME rectifying tower is 150-220 ℃, and the pressure is 0.2-2.2MPa;
the temperature of the top of the methanol rectifying tower (13) is 40-90 ℃, the temperature of the bottom of the tower is 80-150 ℃, and the pressure is 0.1-0.8MPa.
2. The CCUS system for use in the petrochemical industry according to claim 1, wherein: the CO 2 The separator (12) is a membrane separator.
3. The CCUS system for use in the petrochemical industry according to claim 2, wherein: a pump (14) is arranged on a pipeline between a water outlet (13.3) of the methanol rectifying tower (13) and a water inlet (2.7) of the gas steam boiler (2).
4. A CCUS system for use in the petrochemical industry according to claim 1 or 2 or 3, wherein: the absorbent of the absorption tower (8) is methanol.
5. A process for using the CCUS system of any one of claims 1-4 for petroleum and petrochemical industry, comprising the steps of:
1) The air is separated by an air separation device (1) to obtain nitrogen and oxygen-enriched air, the nitrogen is directly reinjected into an oil reservoir to drive oil, and the oxygen-enriched air is introduced into a gas steam boiler (2) to be mixed with natural gas for combustion to obtain steam and flue gas; one part of the steam is injected into an oil reservoir to drive oil, and the other part of the steam is used as supplementary steam for triple reforming reaction; part of the flue gas and the oxygen-enriched gas are mixed and enter a gas steam boiler (2) for recycling, and the other part of the flue gas enters a triple reforming reactor (3) to perform triple reforming reaction with natural gas, oxygen and steam to generate synthesis gas;
2) One part of the synthesis gas obtained by the triple reforming reactor (3) is directly reinjected into an oil reservoir for oil displacement, and the other part of the synthesis gas is subjected to heat exchange with a reaction product obtained after the reaction of the slurry bed reactor (5) by a heat exchanger (4) and then enters the slurry bed reactor (5) for one-step synthesis of DME reaction, wherein the reaction temperature in the slurry bed reactor (5) is 260-270 ℃ and the reaction pressure is 3-5MPa;
3) The reaction product of the slurry bed reactor (5) enters a condenser (6) to be condensed to 30-40 ℃ after heat exchange of a heat exchanger (4), wherein methanol steam and DME steam are condensed into liquid-phase products, and noncondensable gases CO and CO are obtained 2 、H 2 And uncondensed DME gas is used as a gas phase product, the liquid phase product and the gas phase product enter a gas-liquid separator (7) for separation, and the gas phase product enters an absorption tower (8) for absorption by methanol and then is non-condensable gases CO and H 2 Discharging from the top of the absorption tower (8), recycling the synthetic raw material through the pressure swing adsorption device (9), and circularly entering a second pipeline (15.2);
4) The absorption liquid at the bottom of the absorption tower (8) enters a methanol dehydration reactor (10) for reaction to obtain the catalyst containing dimethyl ether, water and CO 2 The product and the liquid phase product of the gas-liquid separator (7) enter a DME rectifying tower (11) together, rectifying and separating are carried out under the pressure of 0.2-2.2MPa, the tower top temperature is 20-90 ℃, the tower bottom temperature is 150-220 ℃, and DME is rectified;
5) The mixed gas obtained by the DME rectifying tower (11) enters CO 2 A separator (12) for separating CO 2 Injecting oil reservoir oil displacement; the crude methanol solution obtained by the DME rectifying tower (11) enters a methanol rectifying tower (13), the methanol and the water are separated by rectifying and separating under the pressure of 0.1-0.8MPa, the methanol returns to the absorption tower (8), and the water is sent into a gas steam boiler (2) by a pump (14) for recycling.
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