CN116694359B - DCC integrated system and method for increasing yield of olefin - Google Patents
DCC integrated system and method for increasing yield of olefin Download PDFInfo
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- CN116694359B CN116694359B CN202210189852.4A CN202210189852A CN116694359B CN 116694359 B CN116694359 B CN 116694359B CN 202210189852 A CN202210189852 A CN 202210189852A CN 116694359 B CN116694359 B CN 116694359B
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 42
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000926 separation method Methods 0.000 claims abstract description 73
- 239000012535 impurity Substances 0.000 claims abstract description 57
- 238000005336 cracking Methods 0.000 claims abstract description 48
- 238000007906 compression Methods 0.000 claims abstract description 41
- 230000006835 compression Effects 0.000 claims abstract description 41
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 38
- 238000004230 steam cracking Methods 0.000 claims abstract description 35
- 238000005194 fractionation Methods 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims description 129
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 42
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000001294 propane Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 24
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 17
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 15
- 239000003502 gasoline Substances 0.000 claims description 12
- 239000001273 butane Substances 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 9
- 230000029936 alkylation Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000001993 dienes Chemical class 0.000 claims description 6
- 238000005057 refrigeration Methods 0.000 claims description 6
- 239000000295 fuel oil Substances 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 125000001741 organic sulfur group Chemical group 0.000 claims description 3
- 230000000750 progressive effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004523 catalytic cracking Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- -1 ethylene, propylene, ethane Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/26—Fuel gas
-
- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of olefin production, and discloses a DCC integrated system and a method for increasing yield of olefin. The DCC cracking unit, the fractionating unit, the compression impurity removal unit and the cryogenic separation unit of the system are sequentially connected; the first outlet of the cryogenic separation unit and the refinery liquefied gas feed line are respectively connected with the inlet of the alkylation reaction unit; the first outlet of the alkylation reaction unit is sequentially connected with inlets of the OCC cracking unit and the compression impurity removal unit; the second outlet of the cryogenic separation unit and the second outlet of the alkylation reaction unit are simultaneously connected with the inlet of the steam cracking unit, and the outlet of the steam cracking unit is connected with the inlet of the fractionation unit; the third outlet of the cryogenic separation unit is connected with the inlet of the PDH unit; the inlet of the compression impurity removal unit is also connected with the outlet of the PDH unit and the mixed dry gas feeding pipeline. The invention takes DCC, light hydrocarbon steam cracking, PDH and OCC as the four heads of raw material cracking, and can prepare olefin from raw materials to the maximum extent.
Description
Technical Field
The invention belongs to the field of olefin production, and in particular relates to a DCC integrated system and a DCC integrated method for increasing yield of olefin.
Background
In the traditional separation process flow of DCC (deep catalytic cracking), the raw material heavy oil is subjected to catalytic cracking to obtain reaction oil gas; the reaction oil gas is fractionated and absorbed stably, and heavy components such as coke, slurry oil, diesel oil, gasoline and the like are removed to obtain light gas and liquid two phases; the two-step process is carried out to obtain LPG and dry gas (the dry gas and the liquefied gas are respectively desulfurized and decarbonized); the liquefied gas after double removal is subjected to gas separation to obtain propylene, propane and mixed C-IV-based liquefied gas, the propylene gas is further refined to obtain a polymerization-grade propylene product, and the propane is subjected to steam cracking to further crack to prepare olefin; concentrating the desulfurized dry gas, and removing methane/hydrogen tail gas through dry gas concentration and impurity removal treatment (oil absorption or PSA) to obtain concentrated mixed carbon secondary dry gas; the concentrated mixed carbon two dry gas is subjected to cryogenic separation to obtain a polymerization grade ethylene product, and the recycle ethane/propane, refinery propane and gas-separation propane which are subjected to cryogenic separation are subjected to a light hydrocarbon steam cracking process to prepare olefin. See fig. 1.
On the other hand, since a small amount of mixed dry gas (refinery FCC dry gas, coked dry gas, etc.) resources from the above-mentioned locations can be recycled together, further dry gas pretreatment (i.e., the above-mentioned impurity removal and dry gas concentration treatment) is also required, and further cryogenic separation is performed to recover ethylene, propylene, ethane and propane. See fig. 1.
The flow is characterized in that: the DCC (deep catalytic cracking) device and the steam cracking device are arranged at the same time to obtain a polymerization grade ethylene product and a polymerization grade propylene product; meanwhile, the dry gas recovery treatment unit has different process routes (oil absorption or PSA), and the loss of carbon two components is 8-17%, so that the recovery rate of olefin in the whole process is low; recycling propane to the steam cracking device, wherein the olefin yield is not maximized; the mixed carbon IV does not further prepare ethylene/propylene, and the comprehensive utilization efficiency of resources is low. After the isobutane is removed by alkylation treatment of the mixed carbon four, the obtained n-butane can be sent to steam cracking to increase the yield of olefin; the residual carbon tetraolefin can increase the yield of propylene and a small amount of ethylene through OCC olefin catalytic cracking, but a compression unit, a cold separation unit and a hot separation unit are required to be arranged to obtain polymerization grade ethylene and polymerization grade propylene. The OCC scale is much smaller than the DCC scale, and the separation device is repeatedly arranged. The prior proposal has the advantages of complicated flow, low recovery rate of polymerized olefin, insufficient comprehensive utilization of whole plant resources, repeated arrangement of partial separation units or equipment, high investment and large management difficulty.
Accordingly, there is a need to propose a new DCC integrated system and method for olefin yield increase.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a DCC integrated system and a DCC integrated method for increasing yield of olefin. The system and the method take DCC (deep catalytic cracking), light hydrocarbon steam cracking, PDH (propane dehydrogenation) and OCC (olefin catalytic cracking) as four heads of raw material cracking, and share one set of fractionation, compression impurity removal and cryogenic separation units to form one tail, so that the raw material can be furthest used for preparing olefin.
In order to achieve the above object, in one aspect, the present invention provides a DCC integrated system for increasing yield of olefins, the system comprising a DCC cracking unit, a fractionation unit, a compression impurity removal unit, a cryogenic separation unit, a steam cracking unit, an alkylation reaction unit, an OCC cracking unit and a PDH unit;
The DCC cracking unit, the fractionating unit, the compression impurity removal unit and the cryogenic separation unit are connected in sequence;
The cryogenic separation unit comprises a plurality of outlets, and a first outlet of the cryogenic separation unit and a refinery liquefied gas feed line are respectively connected with an inlet of the alkylation reaction unit;
The first outlet of the alkylation reaction unit is sequentially connected with the inlets of the OCC cracking unit and the compression impurity removal unit;
The second outlet of the cryogenic separation unit and the second outlet of the alkylation reaction unit are simultaneously connected with the inlet of the steam cracking unit, and the outlet of the steam cracking unit is connected with the inlet of the fractionation unit;
the third outlet of the cryogenic separation unit is connected with the inlet of the PDH unit;
the inlet of the compression impurity removal unit is also connected with the outlet of the PDH unit and a mixed dry gas feeding pipeline.
According to the invention, preferably, the first outlet of the cryogenic separation unit is connected to the inlet of the alkylation reaction unit by a mixed carbon four output line.
According to the present invention, preferably, the first outlet of the alkylation reaction unit is connected to the inlets of the OCC cracking unit and the compression impurity removal unit in sequence through a remaining four-carbon output line.
According to the present invention, preferably, the second outlet of the cryogenic separation unit is connected to the inlet of the steam cracking unit through an ethane recycle line, and the second outlet of the alkylation reaction unit is connected to the inlet of the steam cracking unit through an n-butane output line.
According to the invention, preferably, the third outlet of the cryogenic separation unit is connected to the inlet of the PDH unit by a propane recycle line.
According to the present invention, preferably, the cryogenic separation unit further comprises a cold box, a demethanizer, a deethanizer, an ethylene rectification column, a depropanizer, a propylene rectification column, a debutanizer, an ethylene machine and a propylene machine.
According to the present invention, preferably, the remaining outlets of the cryogenic separation unit are connected to a hydrogen rich gas outlet line, a methane tail gas outlet line, a polymerization stage ethylene outlet line, a polymerization stage propylene outlet line and a crude pyrolysis gasoline outlet line, respectively.
According to the invention, preferably, the third outlet of the alkylation reaction unit is connected to an alkylate output line.
According to the invention, preferably, the OCC cracking unit is further connected to a crude butane output line.
According to the invention, preferably, the fractionation unit is further connected to a heavies output line.
According to the present invention, preferably, the compression impurity removal unit includes a compressor, an amine wash/caustic wash tower, and an impurity removal adsorption bed.
According to the present invention, preferably, a selective hydrogenation device is provided between the cryogenic separation unit and the alkylation reaction unit. In the invention, if the content of diene and alkyne in the mixed carbon four is higher, a carbon four selective hydrogenation device is arranged to meet the feeding requirement of alkylation.
In another aspect, the present invention provides a DCC integrated process for increasing the yield of olefins, the process being carried out in the system, comprising the steps of:
S1: sending the reaction oil gas produced by the DCC cracking unit and the cracking gas from the steam cracking unit into the fractionating unit for fractionation treatment to obtain rich gas and heavy components; the rich gas, crude propylene from the OCC unit, reactor effluent from the PDH unit and mixed dry gas are sent into the compression impurity removal unit together for compression impurity removal treatment, and process gas after impurity removal is obtained;
In the invention, the components and molecular weights of crude propylene and mixed dry gas from the OCC unit are similar to those of rich gas, meanwhile, the gas phase quantity is small relative to the DCC ratio, and the components and molecular weights can be combined into a compression unit to be mixed with the rich gas, so that the subsequent separation system flow and equipment are not greatly influenced, and the components and the molecular weight are treated by removing impurities and recovering olefin, so that the comprehensive utilization efficiency of resources and the recovery rate of olefin can be improved.
S2: delivering the process gas subjected to impurity removal into the cryogenic separation unit for cryogenic progressive separation treatment to obtain polymerization-grade ethylene, polymerization-grade propylene products, hydrogen-rich gas, methane tail gas, mixed carbon four, circulating ethane, circulating propane and crude pyrolysis gasoline;
s3: feeding the mixed C-IV and refinery liquefied gas into the alkylation reaction unit for alkylation treatment to obtain alkylate, n-butane and residual C-IV; sending the n-butane and the circulating ethane into the steam cracking unit for cracking treatment to obtain the cracking gas, and sending the cracking gas into the fractionation unit;
S4: feeding the residual carbon four into the OCC cracking unit to obtain crude propylene and crude butane; feeding said recycled propane and refinery propane to said PDH unit for treatment to obtain said reactor effluent; the crude propylene and the reactor effluent are fed to the compression impurity removal unit.
According to the invention, preferably, the raw material in the DCC cracking unit is hydrogenated wax oil and/or hydrogenated heavy oil.
According to the present invention, preferably, the treatment process of the PDH unit is at least one of fixed bed, moving bed and fluidized bed processes, and preferably, a fluidized bed process is selected.
According to the invention, preferably, the substances removed by the fractionating unit after the gas in the fractionating unit is subjected to the fractionating treatment are heavy components with a distillation range of more than or equal to 150 ℃, and preferably, the substances removed by the fractionating unit comprise coke, slurry oil, diesel oil and pyrolysis gasoline.
According to the invention, preferably, after the gas in the compression impurity removal unit is subjected to the compression impurity removal treatment, the removed impurities include CO 2、H2S、NOx, organic sulfur, arsenic and mercury; the impurity content in the gas treated by the compression impurity removal unit is less than or equal to 1ppm.
According to the present invention, preferably, the outlet pressure of the compressor in the compression impurity removal unit is 0.03 to 4.5mpa g.
According to the present invention, preferably, the mixed dry gas is refinery FCC dry gas and/or coked dry gas.
According to the invention, preferably, the refrigeration capacity of the cryogenic separation unit is provided by overlapping refrigeration of an ethylene machine and a propylene machine.
According to the invention, preferably, the methane-hydrogen tail gas in the cryogenic separation unit is separated at a temperature of-160 to-165 ℃ to obtain the hydrogen-rich gas and part of methane tail gas.
In the cryogenic separation unit, as a preferred scheme, methane tail gas and hydrogen-rich gas are separated at the temperature of-163 ℃, so that hydrogen-rich gas with higher added value, namely 95mol% of H 2/N2, is obtained, and compared with the existing process, hydrogen can be recovered to the greatest extent without Pressure Swing Adsorption (PSA), and a large amount of hydrogen lost by a dry gas recovery unit along with the methane tail gas is reduced.
According to the invention, preferably, the H 2/N2 in the hydrogen-rich gas has a purity of 94-96mol%.
According to the invention, preferably, the remaining methane tail gas in the methane tail gas comes from the demethanizer overhead gas phase.
According to the present invention, it is preferable that the recovery rate of the polymer grade olefin is 99.6% or more; the yield of diene is improved by 50-60%.
In the invention, mixed carbon four and refinery liquefied gas obtained by separation of a cryogenic separation unit are used as alkylation raw materials, and n-butane, residual carbon four olefin and alkylate are obtained after alkylation, wherein:
The alkylate is directly used as a gasoline product;
Recycling ethane obtained by cryogenic separation of n-butane as a cracking raw material to a steam cracking unit for preparing cracking gas by light hydrocarbon steam cracking, and merging the cracking gas into oil gas subjected to DCC cracking;
sending propane obtained by cryogenic separation and refinery propane into a PDH unit;
the residual carbon tetraolefins are subjected to OCC (olefin catalytic cracking) to produce crude propylene and byproduct crude butane; mixing the crude propylene, the mixed dry gas and the rich gas, and compressing to remove impurities.
Therefore, the invention greatly simplifies the flow of recycling ethylene from the DCC reaction gas of deep catalytic cracking, improves the yield of diene by 50-60%, improves the recovery rate of olefin by more than 99.6% from 83-92%, improves the comprehensive utilization efficiency of preparing crude propylene by mixing carbon four, simplifies the process unit flow, reduces the investment cost, and ensures that the final product structure does not contain alkanes such as ethane/propane/butane and the like.
The technical scheme of the invention has the following beneficial effects:
(1) The system and the method take DCC (deep catalytic cracking), light hydrocarbon steam cracking, PDH (propane dehydrogenation) and OCC (olefin catalytic cracking) as the four heads of raw material cracking, and the raw material of the DCC (deep catalytic cracking) is heavy oil, ethane and propane contained in reaction oil gas obtained by cracking cannot be used as raw materials of catalytic cracking after final separation, circulating ethane is used as steam cracking raw materials for preparing olefin, and circulating propane and refinery propane are changed into PDH dehydrogenation from steam cracking, so that the yield of low-carbon olefin is improved to more than 80% from 61%, and the overall utilization efficiency of the raw materials is improved.
(2) The mixed carbon four separated by the cryogenic separation unit is rich in isobutane and mono-olefin, n-butane and the residual carbon four are obtained after alkylation treatment, then the n-butane is sent to steam cracking, and the residual carbon four is converted into crude propylene gas through OCC (olefin catalytic cracking) treatment. The invention can convert C2-C4 alkane into alkene to the maximum extent, and has high comprehensive utilization rate of C2-C4, so that the final product structure does not contain ethane/propane/butane and other alkanes, thereby meeting the requirements of' eating, drying and squeezing.
(3) The system and the method optimize the impurity removal and separation processes, and avoid the loss of the carbon bi-component in the dry gas recovery process (usually adopting modes of oil absorption or PSA and the like, 8-17% of the carbon bi-component is mixed into methane tail gas and cannot be recovered).
(4) The invention can well control the separation index of the rectifying tower under lower operation temperature by the rectification operation of cryogenic separation, and simultaneously, the recovery rate of the polymerization grade ethylene and the polymerization grade propylene is improved, and the loss of saturated alkane such as ethane/propane is reduced, thereby greatly improving the separation efficiency (namely the recovery rate of the polymerization grade olefin and the recovery rate of the diene), improving the ethylene yield from about 3.6 percent to more than 11 percent, the propylene yield from about 16 percent to more than 19 percent, and the recovery rate of the polymerization grade ethylene from 83-92 percent to more than 99.6 percent.
(5) The invention provides a one-tail separation process through flow simplification, and a set of equipment for quenching/fractionation, absorption stabilization, gas separation, dry gas recovery and other units can be omitted, and two-line desulfurization is simplified into one-line desulfurization, so that a one-tail process of fractionation, compression and separation is formed. Thus, the number of equipment is reduced, the investment and occupied area are correspondingly reduced, the complexity of the operation of the device is reduced, and the operation stability of the device is improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
FIG. 1 shows a process flow diagram of a prior art DCC reaction oil gas to produce polymeric olefins.
Fig. 2 shows a process flow diagram of a DCC integrated method for increasing yield of olefins provided in embodiment 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The embodiment provides a DCC integrated system for increasing yield of olefin, as shown in FIG. 2, which comprises a DCC cracking unit, a fractionation unit, a compression impurity removal unit, a cryogenic separation unit, a steam cracking unit, an alkylation reaction unit, an OCC cracking unit and a PDH unit;
The DCC cracking unit, the fractionating unit, the compression impurity removal unit and the cryogenic separation unit are connected in sequence;
The cryogenic separation unit comprises a plurality of outlets, and a first outlet of the cryogenic separation unit is connected with an inlet of the alkylation reaction unit through a mixed carbon four output pipeline; a refinery liquefied gas feed line is also connected to the inlet of the alkylation reaction unit; the second outlet of the cryogenic separation unit is connected with the inlet of the steam cracking unit through an ethane circulating pipeline; the third outlet of the cryogenic separation unit is connected with the inlet of the PDH unit through a propane circulation pipeline;
The cryogenic separation unit further comprises a cold box, a demethanizer, a deethanizer, an ethylene rectifying tower, a depropanizer, a propylene rectifying tower, a debutanizer, an ethylene machine and a propylene machine; the rest outlets of the cryogenic separation unit are respectively connected with a hydrogen-rich gas output pipeline, a methane tail gas output pipeline, a polymerization-stage ethylene output pipeline, a polymerization-stage propylene output pipeline and a crude pyrolysis gasoline output pipeline.
The first outlet of the alkylation reaction unit is sequentially connected with the inlets of the OCC cracking unit and the compression impurity removal unit through a residual carbon four output pipeline; the second outlet of the alkylation reaction unit is connected with the inlet of the steam cracking unit through a normal butane output pipeline; the third outlet of the alkylation reaction unit is connected with an alkylate output line.
The outlet of the steam cracking unit is connected with the inlet of the fractionation unit.
The inlet of the compression impurity removal unit is also connected with the outlet of the PDH unit and a mixed dry gas feeding pipeline.
The fractionation unit is also connected to a heavies output line.
The OCC cracking unit is also connected with a crude butane output pipeline.
The DCC integration method for increasing the yield of olefin in the system comprises the following steps:
s1: taking hydrogenated heavy oil as a raw material of the DCC cracking unit, sending the reaction oil gas produced by the DCC cracking unit and the cracking gas from the steam cracking unit into the fractionating unit for fractionation treatment, and removing heavy components such as coke, slurry oil, diesel oil, pyrolysis gasoline and the like to obtain rich gas and heavy components; the rich gas, crude propylene from the OCC unit, reactor effluent from the PDH unit and mixed dry gas are sent into the compression impurity removal unit together for compression impurity removal treatment, and impurities such as CO 2、H2S、NOx, organic sulfur, arsenic, mercury and the like are removed to obtain process gas after impurity removal; the impurity content in the gas treated by the compression impurity removal unit is less than or equal to 1ppm; the mixed dry gas is refinery FCC dry gas and coking dry gas.
S2: delivering the process gas subjected to impurity removal into the cryogenic separation unit for cryogenic progressive separation treatment to obtain polymerization-grade ethylene, polymerization-grade propylene products, hydrogen-rich gas, methane tail gas, mixed carbon four, circulating ethane, circulating propane and crude pyrolysis gasoline; the refrigeration capacity of the cryogenic separation unit is provided by overlapping refrigeration of an ethylene machine and a propylene machine; separating methane tail gas and hydrogen-rich gas from methane hydrogen tail gas at-163 ℃ to obtain hydrogen-rich gas with higher added value, namely 95mol% of H 2/N2, and part of methane tail gas in the methane tail gas, wherein the rest methane tail gas comes from the top gas phase of the demethanizer.
S3: feeding the mixed C-IV and refinery liquefied gas into the alkylation reaction unit for alkylation treatment to obtain alkylate, n-butane and residual C-IV; sending the n-butane and the circulating ethane into the steam cracking unit for cracking treatment to obtain the cracking gas, and sending the cracking gas into the fractionation unit; the alkylate is directly used as a gasoline product;
S4: feeding the residual carbon four into the OCC cracking unit to obtain crude propylene and crude butane; feeding said recycled propane and refinery propane to said PDH unit for treatment to obtain said reactor effluent; the crude propylene and the reactor effluent are fed to the compression impurity removal unit.
The ethylene yield obtained by the system and the method of the embodiment is improved from 3.6% to more than 11%, the propylene yield is improved from 16% to 21%, namely the diene yield is improved by 55%, and the recovery rate of the polymerized olefin is more than 99.6%.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. The DCC integrated system for increasing the yield of the olefin is characterized by comprising a DCC cracking unit, a fractionation unit, a compression impurity removal unit, a cryogenic separation unit, a steam cracking unit, an alkylation reaction unit, an OCC cracking unit and a PDH unit;
The DCC cracking unit, the fractionating unit, the compression impurity removal unit and the cryogenic separation unit are connected in sequence;
The cryogenic separation unit comprises a plurality of outlets, and a first outlet of the cryogenic separation unit and a refinery liquefied gas feed line are respectively connected with an inlet of the alkylation reaction unit;
The first outlet of the alkylation reaction unit is sequentially connected with the inlets of the OCC cracking unit and the compression impurity removal unit;
The second outlet of the cryogenic separation unit and the second outlet of the alkylation reaction unit are simultaneously connected with the inlet of the steam cracking unit, and the outlet of the steam cracking unit is connected with the inlet of the fractionation unit;
the third outlet of the cryogenic separation unit is connected with the inlet of the PDH unit;
the inlet of the compression impurity removal unit is also connected with the outlet of the PDH unit and a mixed dry gas feeding pipeline;
the first outlet of the cryogenic separation unit is connected with the inlet of the alkylation reaction unit through a mixed carbon four output pipeline;
the first outlet of the alkylation reaction unit is sequentially connected with the inlets of the OCC cracking unit and the compression impurity removal unit through a residual carbon four output pipeline;
The second outlet of the cryogenic separation unit is connected with the inlet of the steam cracking unit through an ethane circulating pipeline, and the second outlet of the alkylation reaction unit is connected with the inlet of the steam cracking unit through a n-butane output pipeline;
The third outlet of the cryogenic separation unit is connected with the inlet of the PDH unit through a propane circulation pipeline;
The cryogenic separation unit further comprises a cold box, a demethanizer, a deethanizer, an ethylene rectifying tower, a depropanizer, a propylene rectifying tower, a debutanizer, an ethylene machine and a propylene machine;
the rest outlets of the cryogenic separation unit are respectively connected with a hydrogen-rich gas output pipeline, a methane tail gas output pipeline, a polymerization-stage ethylene output pipeline, a polymerization-stage propylene output pipeline and a crude pyrolysis gasoline output pipeline;
The third outlet of the alkylation reaction unit is connected with an alkylate output pipeline;
The OCC cracking unit is also connected with a crude butane output pipeline;
the fractionation unit is also connected to a heavies output line.
2. The olefin-increasing DCC integrated system of claim 1, wherein the compression impurity removal unit comprises a compressor, an amine wash/caustic wash column, and a impurity removal adsorbent bed.
3. The olefin-increasing DCC integrated system according to claim 1 or 2, wherein a selective hydrogenation device is provided between the cryogenic separation unit and the alkylation reaction unit.
4. A DCC integrated process for increasing the yield of olefins, the process being carried out in a system according to any of claims 1 to 3, comprising the steps of:
S1: sending the reaction oil gas produced by the DCC cracking unit and the cracking gas from the steam cracking unit into the fractionating unit for fractionation treatment to obtain rich gas and heavy components; the rich gas, crude propylene from the OCC unit, reactor effluent from the PDH unit and mixed dry gas are sent into the compression impurity removal unit together for compression impurity removal treatment, and process gas after impurity removal is obtained;
S2: delivering the process gas subjected to impurity removal into the cryogenic separation unit for cryogenic progressive separation treatment to obtain polymerization-grade ethylene, polymerization-grade propylene products, hydrogen-rich gas, methane tail gas, mixed carbon four, circulating ethane, circulating propane and crude pyrolysis gasoline;
S3: feeding the mixed C-IV and refinery liquefied gas into the alkylation reaction unit for alkylation treatment to obtain alkylate, n-butane and residual C-IV; sending the n-butane and the circulating ethane into the steam cracking unit for cracking treatment to obtain cracking gas, and sending the cracking gas into the fractionation unit;
S4: feeding the residual carbon four into the OCC cracking unit to obtain crude propylene and crude butane; feeding said recycled propane and refinery propane to said PDH unit for treatment to obtain said reactor effluent; the crude propylene and the reactor effluent are fed to the compression impurity removal unit.
5. The DCC integrated olefin yield increasing process of claim 4, wherein the feedstock in the DCC cracking unit is hydrogenated wax oil and/or hydrogenated heavy oil.
6. The olefin-increasing DCC integrated process of claim 4, wherein,
The treatment process of the PDH unit is at least one of fixed bed, moving bed and fluidized bed processes;
after the gas in the fractionating unit is subjected to the fractionating treatment, the removed substances are heavy components with the distillation range of more than or equal to 150 ℃;
after the gas in the compression impurity removal unit is subjected to the compression impurity removal treatment, the removed impurities comprise CO 2、H2S、NOx, organic sulfur, arsenic and mercury; the impurity content in the gas treated by the compression impurity removal unit is less than or equal to 1ppm;
The outlet pressure of the compressor in the compression impurity removal unit is 0.03-4.5 MPaG;
The mixed dry gas is refinery FCC dry gas and/or coking dry gas.
7. The DCC integrated olefin yield increasing process of claim 6, wherein the PDH unit is treated in a fluidized bed process.
8. The olefin-increasing DCC integrated process of claim 6, wherein the material removed by the fractionation unit comprises coke, slurry oil, diesel oil, and pyrolysis gasoline.
9. The olefin-increasing DCC integrated process of claim 4, wherein,
The refrigeration capacity of the cryogenic separation unit is provided by overlapping refrigeration of an ethylene machine and a propylene machine;
Separating methane-hydrogen tail gas in the cryogenic separation unit at the temperature of-160 to-165 ℃ to obtain the hydrogen-rich gas and part of methane tail gas;
the purity of H 2/N2 in the hydrogen-rich gas is 94-96mol%;
The remaining methane tail gas in the methane tail gas comes from the demethanizer overhead gas phase.
10. The DCC integrated olefin yield increasing method according to any one of claims 4 to 9, wherein the recovery rate of the polymerized olefin is 99.6% or more; the yield of diene is improved by 50-60%.
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| CN109678633A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of utilization method of richness butane/pentane saturated hydrocarbons |
| WO2021237483A1 (en) * | 2020-05-25 | 2021-12-02 | 上海卓然工程技术股份有限公司 | Process method and system for co-production of propane dehydrogenation unit and ethylene unit |
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| CN109678633A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of utilization method of richness butane/pentane saturated hydrocarbons |
| WO2021237483A1 (en) * | 2020-05-25 | 2021-12-02 | 上海卓然工程技术股份有限公司 | Process method and system for co-production of propane dehydrogenation unit and ethylene unit |
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