CN110437867A - Method for producing high value-added product by using liquefied gas - Google Patents
Method for producing high value-added product by using liquefied gas Download PDFInfo
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- CN110437867A CN110437867A CN201810415637.5A CN201810415637A CN110437867A CN 110437867 A CN110437867 A CN 110437867A CN 201810415637 A CN201810415637 A CN 201810415637A CN 110437867 A CN110437867 A CN 110437867A
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- liquefied gas
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- high value
- value added
- production high
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 185
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 101
- 238000000034 method Methods 0.000 claims abstract description 76
- 239000000047 product Substances 0.000 claims abstract description 61
- 230000003197 catalytic effect Effects 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 36
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 33
- 230000029936 alkylation Effects 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 24
- 238000006266 etherification reaction Methods 0.000 claims abstract description 23
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000006227 byproduct Substances 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 110
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 86
- 229910052799 carbon Inorganic materials 0.000 claims description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 81
- 239000003054 catalyst Substances 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 238000002156 mixing Methods 0.000 claims description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 45
- 239000001294 propane Substances 0.000 claims description 44
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 36
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 29
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 28
- 229930195733 hydrocarbon Natural products 0.000 claims description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 239000001282 iso-butane Substances 0.000 claims description 20
- 235000013847 iso-butane Nutrition 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 19
- 238000003808 methanol extraction Methods 0.000 claims description 18
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- 238000004523 catalytic cracking Methods 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 108010001267 Protein Subunits Proteins 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 210000004556 brain Anatomy 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 238000005194 fractionation Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 13
- -1 polypropylene Polymers 0.000 abstract description 7
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 239000003254 gasoline additive Substances 0.000 abstract 1
- 235000013844 butane Nutrition 0.000 description 16
- 238000004821 distillation Methods 0.000 description 15
- 239000001273 butane Substances 0.000 description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 12
- 238000011049 filling Methods 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 239000003502 gasoline Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 6
- 238000001802 infusion Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- 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
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- 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
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/86—Chromium
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for producing high value-added products by using liquefied gas, which adopts the process combination of etherification technology, alkylation technology, aromatization technology and catalytic dehydrogenation technology to directly produce MTBE, alkylate, aromatization oil and propylene, and simultaneously produces hydrogen as a byproduct. The MTBE, the alkylate and the aromatized oil can be used as high-octane gasoline additive components, propylene can provide raw materials for downstream polypropylene devices, and the byproduct hydrogen can be used by other hydrogen consumption devices, so that the additional value of the liquefied gas is further improved. The method has the advantages of simple process flow, low dry gas yield and high product yield, and improves the utilization rate of liquefied gas resources.
Description
Technical field
Methyl tertiary butyl ether(MTBE) (MTBE), alkylate oil, aromatization carburetion, third are produced using liquefied gas the present invention relates to a kind of
Alkene, while by-product hydrogen method.Specifically, this method be it is a kind of using etherification technology, alkylation techniques, aromatization technology with
The process combination that catalytic dehydrogenation technology combines, the directly method of production MTBE, alkylate oil, propylene and hydrogen, this method energy
Compared with limits using each component in liquefied gas, realize that the maximum of liquefied gas resource utilizes by process combination.
Background technique
Refinery catalytic cracking gas separation unit, ethylene cracker and a large amount of liquefied gas of light ends unit by-product, liquefied gas
Main component include propylene, propane, normal butane, iso-butane, isobutene, 1- butylene, 2- butylene and a small amount of light dydrocarbon hydrocarbon etc..Mesh
Before, China comprehensively utilizes the opposite shortage of industrial technology of liquefied gas, and some enterprises, which remove, produces methyl tertiary butyl ether(MTBE) using liquefied gas
(MTBE) outside, most of liquefied gas dispatches from the factory as domestic fuel, causes the huge wasting of resources.Therefore, liquefied gas is use up can
The petrochemicals of conversion high added value more than energy can make full use of liquefied gas resource, improve energy utilization rate.
CN201110319824.1 discloses a kind of method by liquefied gas production aromatic hydrocarbons and alkene, and this method utilizes liquefaction
Alkene in gas carries out aromatization, then by aromatization products propane and butane separate, the propane isolated and
Butane carries out dehydrogenation reaction, produces propylene and butylene product.Deficiency existing for this method is when aromatics yield is higher, and dry gas produces
Measure relatively large, olefin yields are not high.
CN201210186746.7 discloses a kind of liquefied gas alkane aromatization and combines production higher octane with alkene aromatisation
It is worth the method for clean gasoline.This method loads alkane aromatization catalyst in reactor upper end, and lower end filling alkene aromatisation is urged
Agent, final products are aromatic naphtha.The deficiency of this method is that product is single, and needs to load two kinds of differences in a reactor
Catalyst, the problem for be easy to causeing operation control difficult.
CN201510699100.2 discloses a kind of method of modified liquefied gas through aromatization.This method passes through virtue for the first time
After structureization reaction, aromatisation product is carried out aromatization again keeps product as much as possible by aromatization twice
Output propane.This method the problem is that, although purified propylene oxide is higher after aromatization twice, the added value of propane
It does not get a promotion further, the outlet of propane is still to carry out being mixed and made into motor liquified gas with a certain proportion of carbon four.
CN201010256506.0 discloses a kind of mixing carbon four using method, main to be handed over using mixing carbon four in cation
It changes in the presence of resin and carries out etherification reaction with methanol, generate MTBE and the mixing carbon four without isobutene, isobutene will be free of
It mixing carbon four and carries out extracting rectifying, obtain mixed butanes and mixed butene, mixed butanes produces propane and aromatic hydrocarbons through catalyzed conversion,
Mixed butene and ethylene carry out disproportionated reaction and produce propylene.
CN201210137002.6 discloses a kind of method for improving mixing four utility value of carbon, and this method is with cracking c_4
For raw material, carries out selective hydrogenation and removes alkynes, wherein vinylacetylene and 1- butine is made to be hydrogenated to 1,3-butadiene and 1- butylene,
By product through extracting rectifying, 1,3-butadiene is isolated.Remaining four logistics of carbon is mixed with refinery C four carries out hydroisomerizing, will
1- isomerization of butene therein is 2- butylene, and its product is separated, and obtains isobutene product.Residue stream is disproportionated
Reaction production propylene, unreacted ethylene and carbon four are used as ethylene cracking material after carrying out full hydrogenation reaction after separation.
CN201611002809.3 discloses a kind of method of carbon four and naphtha aromtization clean gasoline after ether, the party
Method is mixed using the naphtha after being dehydrated and taking off basic nitrogen with carbon four after the ether after methanol removal, is reacted after heating,
Reaction product through weight knockout drum, reaction solution knockout drum, de- heavy aromatics tower, absorb Analytic Tower and stabilizer separation and purification after,
Finally obtain aromatisation gasoline.
CN201620571171.4 discloses a kind of hydrocarbons fluidised-bed aromatisation device of low-carbon.The fluidized bed plant is by being used for
The aromatization of lower carbon number hydrocarbons first converts alkene for lower carbon number hydrocarbons, then carries out aromatization.It is disadvantageous in that and produces dehydrogenation
Object is sent to aromatisation, and process flow is complex, and plant investment is larger.
CN201610420079.2 discloses a kind of lower carbon number hydrocarbons fluidized bed aromatisation device and application.The invention is first by low-carbon
Hydrocarbon is converted into alkene, then carries out aromatization；Or aromatisation is gone again after hydrocarbon that aromatisation is separated carried out dehydrogenation.Work as virtue
When hydrocarbon yield is higher, the yield of dry gas is also relatively high.
By analysis the above-mentioned published patent document it is found that being directed to the utilization of liquefied gas resource substantially, but utilize
Main purpose is mostly to produce aromatisation using mixing carbon four using isobutene production etherified gasoline in mixing carbon four, or further
The chemical products such as gasoline and 1,3-butadiene, 1- butylene and 2- butylene.Above method is the problem is that each in liquefied gas
A component is not taped the latent power its utility value as far as possible, and the effect of comprehensive utilization is poor.
Summary of the invention
High value added product method is produced using liquefied gas the purpose of the present invention is to propose to a kind of, makes full use of liquefied gas raw
Produce the process combination of MTBE, alkylate oil, aromatization carburetion, propylene and by-product hydrogen.This method realizes having for liquefied gas resource
Effect utilizes, and improves the added value of liquefied gas resource.
Process flow of the invention mainly includes depropanization unit, gas sub-unit, etherificate unit, alkylation, aromatization
Change unit, catalytic dehydrogenation unit, mainly comprises the steps that
(1) depropanization unit includes a depropanizing tower, and effect is that (logistics a) is separated into 1 (object of propane by liquefied gas raw material 1
Stream b) with four (logistics c) of depropanization mixing carbon.
(2) (after logistics d) is after the separation of gas sub-unit, propylene (logistics e), (the logistics f) of propane 2 can be obtained in liquefied gas raw material 2
Gentle point of mixing carbon four (logistics g).
(3) by gas point mixing carbon four, ((logistics h) is mixed logistics g), is preheated after mixing, is sent later to etherificate with methanol
Reactor, etherification product (logistics i) after catalytic distillation tower, obtain unreacted carbon four (logistics j) and MTBE (and logistics k), not
(logistics j) enters methanol extraction tower to the carbon four of reaction, carries out methanol extraction by extractant of water, obtains (the logistics l) of carbon four after ether
With mixture (the logistics m) of water and methanol.
By step (1) in obtain depropanization mixing carbon four (logistics c) is divided into two streams in proportion, logistics c1 and
Logistics c2.Wherein (logistics l) is mixed logistics c1, is sent jointly to alkylation reactor, in the work of catalyst with carbon four after ether
Under, isobutane and butene is alkylated reaction.After reaction, by alkylate, (logistics n) is sent into alkylate
Knockout tower obtains alkylate oil (logistics o) and alkylation tail gas (logistics p).
By step (4) in logistics c2 and alkylation tail gas (logistics p) is sent together to aromatization reactor, in catalyst
Under the action of, butane carries out aromatization, and by aromatization products, (logistics q) send to aromatization products and separates after reaction
Tower obtains aromatization carburetion (logistics r) and aromatisation tail gas (logistics s).
By step (1) obtained in propane 1 (logistics b) and step (2) obtained in propane 2 (logistics f) and step (5) in
Obtain aromatisation tail gas (logistics s) is sent jointly to catalytic dehydrogenation unit, and propane carries out dehydrogenation reaction under the effect of the catalyst,
Propylene (logistics t) while by-product hydrogen can be obtained.
Wherein: the sum of 1 iso-butane of liquefied gas raw material and normal butane are not less than 40%, preferably not below 45%.Liquefied gas is former
Isobutene content is not less than 10%, preferably not below 11% in material 2, and iso-butane content is not less than 13%, preferably not below 15%.
Liquefied gas raw material 1 of the present invention is preferably one or both of lighter hydrocarbons liquefied gas, hydrogen recycling liquefied gas.
Liquefied gas raw material 2 of the present invention is preferably refinery catalytic cracking liquefied gas.
Lighter hydrocarbons liquefied gas of the present invention is to strip tower overhead gas, diesel oil hydrogenation stripper with isomerization dry gas, residual hydrogenation
Top gas is hydrocracked stripping tower overhead gas, petroleum naphtha hydrogenation reaction product, is hydrocracked stripping liquid of top of the tower, is hydrocracked fractionating column
The product that the mixture of one or more of top liquid, reformation liquefied gas is obtained through light ends unit.In lighter hydrocarbons liquefied gas most
Good iso-butane content is not less than 25%, is more preferably not less than 30%；Normal butane content is not less than 30%, is more preferably not less than 35%.
Hydrogen of the present invention recycling liquefied gas is with catalysis drying gas, raffinates oil that one such or two kinds are raw material warp
The liquefied gas of hydrogen gas recovering device output.Hydrogen recycles best iso-butane content in liquefied gas and is not less than 28%, is more preferably not less than
30%；Normal butane content is not less than 12%, is more preferably not less than 15%.
Specific implementation method can be with are as follows:
(1) by liquefied gas raw material 1, (logistics a) is sent into depropanizing tower to step, and depropanizing tower uses plate column, liquefied gas raw material 1
Separation product be propane 1 (logistics b) and four (logistics c) of depropanization mixing carbon.The yield of propane is not preferably low not less than 99%
In 99.5%.
(2) by liquefied gas raw material 2, (logistics d) send to gas sub-unit and separates step, obtains propylene (logistics e), propane
(gentle point of mixing carbon four (logistics g) of logistics f).(logistics g) yield is not less than 99%, preferably 99.5% to gas point mixing carbon four.
Step (3) in etherificate unit be made of methyltertiarvbutyl ether reactor, catalytic distillation tower and methanol extraction tower.Methyltertiarvbutyl ether reactor
Using fixed bed reactors, the number of fixed bed reactors is one or two.When using two fixed bed reactors, point
Mode for cloth is serial or parallel connection, and is realized by following connection type: with valve and pipeline by the upper of two fixed bed reactors
Portion is sequentially connected with top, lower part and lower part, top and lower part, and the series connection of two fixed bed reactors is realized by valve transfer
Or it is in parallel, schematic diagram is as shown in Figure 2.When two fixed bed reactors are connected, the depth of etherification reaction progress can be increased, when simultaneously
When connection, can online feed switched, complete catalyst replace online.Filling etherificate is urged respectively in methyltertiarvbutyl ether reactor and catalytic distillation tower
Agent, in 10~80 DEG C of reaction temperature, preferably 25~50 DEG C, reaction pressure is 0.01~3.0MPa, preferably 0.05~
1.5MPa, alcohol hydrocarbon ratio (mass ratio of methanol and hydrocarbon feed) carry out ether under conditions of being 0.1~1.0, preferably 0.15~0.5
Change.((mixture of logistics h) is fed logistics g) gas point mixing carbon four by fixed bed bottom, by the ether at the top of fixed bed with methanol
Changing product, (logistics i) introduces catalytic distillation tower.In catalytic distillation tower in addition to equipped with macroporous cation exchange resin catalyst, also fill
There is filler.Therefore, the separation of etherification reaction and etherification product can be carried out simultaneously in catalytic distillation tower, catalytic distillation column overhead obtains
To unreacted carbon four, (logistics j), tower reactor obtains MTBE, and (purity of logistics k), MTBE are not less than 98%.Due to catalytic distillation tower
The unreacted carbon four that tower top obtains (contains a certain amount of methanol, this strand of material need to be introduced methanol extraction tower and carried out in logistics j)
Methanol extraction, using water as extractant, extraction tower feeding temperature be 20~70 DEG C, preferably 30~60 DEG C, pressure be 0.1~
2.0MPa, preferably 0.5~1.5MPa.(mixture (the logistics of logistics l) He Shuiyu methanol of carbon four after ether is obtained after methanol extraction
m).In the mixture of water and methanol, methanol content control is being not higher than 30%, is preferably not higher than 25%.
The catalyst for etherification that catalyst for etherification uses for this field, such as macroporous cation exchange resin catalyst, quality are complete
Exchange capacity is 2~10mmol/g, and water content is 1~9%, and wet apparent density is 0.6~1.5g/ml.
The present invention does not limit methanol extraction tower type, can be plate column or packed tower.
Step (4) in alkylated reaction unit include alkylation reactor and alkylate knockout tower.By step (1) in
(logistics c) is divided into two streams, respectively logistics c1 and object to depropanization mixing carbon four obtained in depropanizing tower by a certain percentage
Flow c2.Logistics c1 accounts for depropanization mixing carbon four (the 25~35% of the gross mass of logistics c), preferably 27~30%.Logistics c1 with
Step (3) in carbon four after ether (the common alkylation reactor of being sent into of logistics l) mixing is in reaction temperature under the effect of the catalyst
0.1~20 DEG C, preferably 2~10 DEG C, reaction pressure is 0~10MPa, under conditions of preferably 0.5~2.0MPa, iso-butane with
Butylene is alkylated reaction, and by alkylate, (logistics n) is sent into alkylate knockout tower, obtains alkyl after reaction
Carburetion (logistics o) and alkylation tail gas (logistics p).The main component of alkylate oil is trimethylpentane (TMP) and (DMH), is ground
Study carefully method octane number (RON) about 95, (main component of logistics p) is butane to alkylation tail gas.
Catalyst in alkylation reactor is the art alkylation catalyst, preferably liquid acid catalyst,
Such as sulfuric acid or hydrofluoric acid.
Step (5) in aromatization unit include aromatization reactor and aromatization products knockout tower.By logistics c2 with
Alkylation tail gas (logistics p) is sent together to aromatization reactor, and under the effect of the catalyst, reaction temperature is 300~600 DEG C,
It is preferred that 350~550 DEG C, 0.05~4.0MPa of pressure, preferably 0.08~4.0MPa, 0.01~10h of liquid hourly space velocity (LHSV)-1, preferably 0.05
~5h-1Under the conditions of, aromatization occurs for butane, and (logistics q), aromatisation oil content are not less than 22% in aromatization products.Virtue
Structure product after separation, obtains aromatization carburetion (logistics r) and aromatisation tail gas (logistics s), the organon octane of aromatization carburetion
It is worth (RON) up to 90 or more.
Catalyst in aromatization reactor is the art aromatized catalyst, preferably molecular sieve catalyst,
Such as ZSM-5 or metal-modified HZSM-5 molecular sieve catalyst.
(6) step is catalytic dehydrogenation unit, by step (1) obtained in propane 1 (logistics b) and step (2) obtained in propane
2 (logistics f) and step (5) obtained in aromatisation tail gas (logistics s) is sent jointly to catalytic dehydrogenation unit.Aromatisation tail gas (logistics
S) main component is propane.
The catalyst used in catalytic dehydrogenating reaction device is this field dehydrogenation, such as platinum group or chromium-based catalysts.
Dehydrogenation is with Al2O3For carrier, the active component of load can be one of Pt, Cr, Mo, V element or several
Kind, the auxiliary agent of load is one or more of Ni, Cu, Ca, Mg, K element.It is prepared preferably by coprecipitation or infusion process
Catalyst.When making to prepare catalyst using coprecipitation, properly mixed nitrate is dissolved in deionized water, is vigorously stirred lower drop
Add ammonium hydroxide/ammonium carbonate, 3~48h of aging.Then it is filtered, washed, dried and roasted, form catalyst.It is prepared using infusion process
When catalyst, the nitrate of properly mixed aluminium and active component is dissolved in a certain amount of deionized water, carrier is added, 40
It is slowly dried under the conditions of~150 DEG C, then through drying, predecomposition, roasting, obtains catalyst.Dehydrogenation vector contg 50
~90%, active component constituent content 1~40%, auxiliary element content 0.1~30%.
The catalytic dehydrogenating reaction condition that the present invention recommends is: reaction temperature be 400~800 DEG C, preferably 500~700 DEG C,
Reaction pressure is 0~1MPa, and preferably 0.1~0.5MPa, Feed space velocities are 1.0~6.0h-1, preferably 1.0~4.0h-1.It should
The best conversion of propane of process is 30~50%, and Propylene Selectivity is 60~80%.
Catalytic dehydrogenating reaction device of the present invention can be fixed bed reactors or fluidized-bed reactor.
The catalyst that catalytic dehydrogenation unit uses can be the extruded catalyst or suitable fluidized bed for being suitble to fixed bed
Microspherical catalyst.According to the difference of catalyst form, fixed bed reactors or fluidized-bed reactor is may be selected in dehydrogenation reactor.
The work that the method for the present invention is combined using etherification technology, alkylation techniques, aromatization technology with catalytic dehydrogenation technology
Skill combination, can directly produce MTBE, alkylate oil, aromatization carburetion and propylene, while by-product hydrogen.This method can be compared with limits
Using each component in liquefied gas, realize that the maximum of liquefied gas resource utilizes by process combination.The invention has the characteristics that
(1) the present invention can make full use of the rich content mixing carbon four in liquefied gas, be etherified using isobutene and methanol
Reaction generates MTBE, is alkylated reaction using isobutane and butene and generates alkylate oil and butane aromatisation generation aromatisation
Oil, three of the above product can be used as high-knock rating gasoline addO-on therapy.
(2) the present invention utilizes the propane and aromatisation list isolated from lighter hydrocarbons liquefied gas, hydrogen gas recovering device liquefied gas
The aromatisation tail gas of member production carries out dehydrogenation reaction, generates propylene, can provide raw material for downstream polypropylene plant, while going back by-product
The hydrogen of a certain amount of hydrogen, by-product uses for other consumption hydrogen production devices, therefore improves the added value of liquefied gas.
(3) the present invention passes through etherification technology, alkylation techniques, aromatization technology and the combination of catalytic dehydrogenation technical matters, technique
Process is simple, and dry gas yied is low, and product yield is high, realizes the optimum utilization of liquefied gas resource.
Detailed description of the invention
Fig. 1 is using a kind of process flow chart of the invention.
In Fig. 1: 1- gas sub-unit, 2- methyltertiarvbutyl ether reactor, 3- catalytic distillation tower, 4- methanol extraction tower, 5- alkylated reaction
Device, 6- alkylate knockout tower, 7- aromatization reactor, 8- aromatization products knockout tower, 9- depropanizing tower, 10- catalysis are de-
Hydrogen unit.
Logistics a- liquefied gas raw material 1；Logistics b- propane 1；Logistics c- depropanization mixing carbon four；Logistics d- liquefied gas raw material 2；
Logistics e- propylene；Logistics f- propane 2；Logistics g- gas point mixing carbon four；Logistics h- methanol；Logistics i- etherification product；Logistics j- is not
The carbon four of reaction；Logistics k-MTBE；Carbon four after logistics l- ether；The mixture of logistics m- water and methanol；Logistics n- alkylate；
Logistics o- alkylate oil；Logistics p- is alkylated tail gas；Logistics q- aromatization products；Logistics r- aromatization carburetion；Logistics s- aromatisation
Tail gas；Logistics t- propylene.
Fig. 2 is connected mode schematic diagram when present invention etherificate unit uses two fixed bed reactors.
In figure, 1# and 2# are fixed bed reactors respectively.
Specific embodiment
Embodiment 1
With catalytic cracking liquefied gas, lighter hydrocarbons recovery liquefied gas and hydrogen recycling liquefied gas are raw material, and raw material composition is shown in Table 1.
By catalytic cracking liquefied gas, that is, liquefied gas raw material 2, (logistics d) is sent into gas sub-unit 1, and propylene (object is obtained after gas sub-unit 1
Stream is e), ((logistics g), (logistics g) composition is shown in Table 2 to gas point mixing carbon four to gentle point of mixing carbon four of logistics f) to propane 2, and lighter hydrocarbons are returned
Receipts liquefied gas and hydrogen recycling liquefied gas are mixed into liquefied gas raw material 1, and (logistics a) is sent into depropanizing tower 9, obtains 1 (logistics of propane
B) (logistics c), logistics c composition are shown in Table 3 with depropanization mixing carbon four.
1 raw material of table composition
2 gas of table point mixing carbon four forms table
3 depropanization mixing carbon four of table forms table
| Mix four component of carbon | Content/wt% |
| Iso-butane | 45.42 |
| Normal butane | 49.88 |
| N-butene | 0.13 |
| Isobutene | 0.42 |
| Anti- butylene | 0.11 |
| Maleic | 0.23 |
| C5+ (contains isopentane) | 3.89 |
| It is total | 100.00 |
By gas point mixing carbon four, ((logistics h) is mixed to be sent to methyltertiarvbutyl ether reactor 2 logistics g), and methyltertiarvbutyl ether reactor 2 uses with methanol
One fixed bed reactors under the conditions of alcohol hydrocarbon ratio is 0.45, is etherified at 40 DEG C of reaction temperature, reaction pressure 0.8MPa
Reaction, (logistics h) property is shown in Table 4 to methanol.By the etherification product after reaction, (logistics i) is sent into catalytic distillation tower 3.
Macropore cation resin catalyst is loaded respectively in methyltertiarvbutyl ether reactor 2 and catalytic distillation tower 3.In methyltertiarvbutyl ether reactor 2
Catalyst segments filling, has reserved expansion space of the catalyst under reactiveness, has preferably avoided being emerged for hot spot.Catalysis
Filler is also equipped in addition to loading catalyst for etherification in destilling tower 3.Catalyst packing is extremely in catalytic distillation tower 3
In filling component in ZL201520508723.2 in embodiment 1.The quality full exchange capacity of catalyst for etherification be 2~
10mmol/g, water content are 1~9%, and wet apparent density is 0.6~1.5g/ml.
3 tower top of catalytic distillation tower obtains unreacted carbon four, and (logistics j), tower reactor obtain MTBE (logistics k).Unreacted carbon
Four (logistics j) enter methanol extraction tower 4 carry out methanol extraction, feeding temperature be 45 DEG C, pressure 0.8MPa, methanol extraction tower 4
Using plate column, extractant is water.4 tower top of methanol extraction tower is (logistics l), (methanol in logistics l) of carbon four after ether of carbon four after ether
Content is not higher than 1%, and tower reactor is that ((methanol contains the mixture of logistics m), water and methanol in logistics m) for the mixture of water and methanol
Amount is 18.6%.
4 methanol of table meets GB 338-2004 (Grade A) index
By depropanization mixing carbon four, (logistics c) is divided into two logistics: logistics c1 and logistics c2, the present embodiment by a certain percentage
The ratio of middle logistics c1 and logistics c2 is 1:2.6, i.e. logistics c1 accounts for four (the 27.8% of logistics c) of depropanization mixing carbon.Wherein object
Flowing c1, (logistics l) is mixed, and is sent jointly to alkylation reactor 5, and reaction is alkylated with carbon four after ether.
Catalyst system is sulfuric acid in alkylation reactor 5, and reaction feed is 8 DEG C, reaction pressure 1MPa, iso-butane and fourth
Allylic alkylationization reaction, butene conversion are not less than 98.5%, and by alkylate, (logistics n) introduces alkylation and produces after reaction
Object knockout tower 6, alkylate knockout tower 6 use plate column, and tower top is that (logistics p) is alkylated tail gas (logistics to alkylation tail gas
P) main ingredient is butane, wherein butane content 74%.Tower reactor is alkylate oil (logistics o), the alkylate oil (master of logistics o)
Will group be divided into trimethylpentane and dimethylhexane.
Tail gas will be alkylated, and (logistics p) and logistics c2 are mixed and are sent into aromatization reactor 7 jointly, aromatized catalyst use
The aromatized catalyst SIHZSM-5 (A) -01 prepared using the Catalyst Preparation Example 7 in patent CN1586721A, anti-
Answering temperature is 430 DEG C, reaction pressure 3.0MPa, air speed 2.5h-1Under conditions of, carry out aromatization.Aromatization products (object
Stream q) obtains aromatization carburetion (logistics r) and aromatisation tail gas (logistics s), aromatisation tail after the separation of aromatization products knockout tower 8
(propane content is 96.8% to gas in logistics s).
By propane 1, (((logistics s) is sent into catalytic dehydrogenation unit 10 jointly for logistics f) and aromatisation tail gas for logistics b), propane 2
Carry out catalytic dehydrogenating reaction.Catalytic dehydrogenation unit 10 uses fixed bed reactors, interior filling catalytic dehydrogenation catalyst.Catalytic dehydrogenation
Catalyst is with Al2O3For carrier, load C r, Ni, Cu, Ca element is prepared, catalyst carrier content 85% using coprecipitation, living
Property constituent content 10%, auxiliary agent content 5%.Catalytic dehydrogenating reaction is 605 DEG C, reaction pressure 0.2MPa in temperature, and air speed is
2.5h-1Under conditions of carry out, propylene (logistics obtained in the dehydrogenation product obtained through catalytic dehydrogenation unit 10 and gas sub-unit 1
E) it mixes, obtains propylene (logistics t).
The mass yield of system each component in process are as follows: dry gas 4.77%, propylene 35.98%, propane 17.66%,
MTBE10.57%, alkylate oil 24.50%, aromatization carburetion 6.27%, wherein hydrogen accounts for 79.04vol% in dry gas.
Embodiment 2
With catalytic cracking liquefied gas, that is, liquefied gas raw material 2 (logistics d) and lighter hydrocarbons recovery liquefied gas, that is, 1 (object of liquefied gas raw material
Stream a) is raw material, and raw material composition is shown in Table 1, and (logistics h) feedstock property is shown in Table 4 to methanol.Process flow and embodiment 1 in embodiment 2
It is identical.(logistics g) composition is shown in Table 5 to gas point mixing carbon four, and (logistics c) composition is shown in Table 6 to depropanization mixing carbon four.
5 gas of table point mixing carbon four forms table
| Mix four component of carbon | Content/wt% |
| Iso-butane | 28.00 |
| Normal butane | 6.40 |
| N-butene | 14.00 |
| Isobutene | 25.00 |
| Anti- butylene | 14.00 |
| Maleic | 8.00 |
| C5+ (contains isopentane) | 4.60 |
| It is total | 100.00 |
6 depropanization mixing carbon four of table forms table
| Mix four component of carbon | Content/wt% |
| Iso-butane | 44.00 |
| Normal butane | 51.00 |
| N-butene | 0.10 |
| Isobutene | 0.50 |
| Anti- butylene | 0.18 |
| Maleic | 0.25 |
| C5+ (contains isopentane) | 4.00 |
| It is total | 100.00 |
Embodiment 2 is difference from example 1 is that the following aspects:
1. 48 DEG C of etherification reaction temperature, reaction pressure 1.0MPa, under the conditions of alcohol hydrocarbon ratio is 0.48, carrying out etherification reaction.
Catalyst loading pattern is in catalytic distillation tower 3, and catalyst is filled to after being wrapped up using special cloth bag
In filling component in ZL201520508723.2 in embodiment 1.In methanol extraction tower 4, unreacted four (logistics j) charging of carbon
Temperature is 48 DEG C, pressure 0.9MPa, and tower reactor is mixture (mixture (the logistics m) of logistics m), water and methanol of water and methanol
The content of middle methanol is 17.9%.
2. catalyst system is sulfuric acid in alkylation reactor 5, reaction feed temperature is 5 DEG C, reaction pressure 0.8MPa.It is different
Butane and butene alkylation, butene conversion are not less than 99%, and 6 tower top of alkylate knockout tower obtains alkylation tail gas
(logistics p), wherein butane content 71%.
3. aromatized catalyst uses the aromatisation prepared using the Catalyst Preparation Example 7 in patent CN1586721A
Catalyst SIHZSM-5 (A) -02 is 440 DEG C, reaction pressure 2.5MPa, air speed 2.5h in reaction temperature-1Under conditions of, into
Row aromatization.Aromatization products (logistics q) through aromatization products knockout tower 8 separation after obtain aromatization carburetion (logistics r) and
(logistics s), (propane content is 96% to aromatisation tail gas to aromatisation tail gas in logistics s).
4. catalytic dehydrogenation unit 10 uses fluidized-bed reactor, catalyst is microspherical catalyst.With Al2O3For carrier, load
Cr, Ni, Cu, Ca, K element, are prepared using infusion process, vector contg 82%, active component content 15%, auxiliary agent content 3%.
It is 600 DEG C, reaction pressure 0.15MPa, air speed 2.0h in reaction temperature-1Under conditions of carry out dehydrogenation reaction.
The mass yield of system each component in process are as follows: dry gas 4.45%, propylene 36.55%, propane 16.47%, MTBE
11.30%, alkylate oil 25.14%, aromatization carburetion 6.09%, wherein hydrogen accounts for 79.05vol% in dry gas.
Embodiment 3
With catalytic cracking liquefied gas, that is, liquefied gas raw material 2, (logistics d) and hydrogen recycle liquefied gas, that is, 1 (object of liquefied gas raw material
Stream a) is raw material, and raw material composition is shown in Table 1, and (logistics h) feedstock property is shown in Table 4 to methanol.Process flow and embodiment 1 in embodiment 3
It is identical.(logistics g) composition is shown in Table 7 to gas point mixing carbon four, and (logistics c) composition is shown in Table 8 to depropanization mixing carbon four.Embodiment 3 and reality
Example 1 is applied the difference is that the following aspects:
1. 48 DEG C of etherification reaction temperature, reaction pressure 0.9MPa, under the conditions of alcohol hydrocarbon ratio is 0.4, carrying out etherification reaction.It will
Catalyst is filled in ZL201520508723.2 catalyst in embodiment 1 and filled after being loaded using special stainless steel network structure
It fills out in component, is packed into catalytic distillation tower 3.In methanol extraction tower 4, (logistics j) feeding temperature is 50 DEG C to unreacted carbon four, pressure
For 0.7MPa, tower reactor is that ((content of methanol is the mixture of logistics m), water and methanol in logistics m) for the mixture of water and methanol
22.2%.
2. catalyst system is sulfuric acid in alkylation reactor 5, reaction feed temperature is 4 DEG C, reaction pressure 0.9MPa.It is different
Butane and butene alkylation, butene conversion are not less than 99%, and 6 tower top of alkylate knockout tower must be alkylated tail gas
(logistics p), wherein butane content 35%.
3. aromatized catalyst uses the aromatisation prepared using the Catalyst Preparation Example 7 in patent CN1586721A
Catalyst SIHZSM-5 (A) -03 is 435 DEG C, reaction pressure 3.0MPa, air speed 2.0h in reaction temperature-1Under conditions of, into
Row aromatization.Aromatization products (logistics q) through aromatization products knockout tower 8 separation after obtain aromatization carburetion (logistics r) and
(logistics s), (propane content is 95% to aromatisation tail gas to aromatisation tail gas in logistics s).
4. catalytic dehydrogenation unit 10 uses fluidized-bed reactor, catalyst is microspherical catalyst.With Al2O3For carrier, load
Cr, Ni, Cu, Ca, Mg element, are prepared using infusion process, vector contg 85%, active component content 12%, auxiliary agent content
3%.It is 590 DEG C, reaction pressure 0.12MPa, air speed 2.5h in reaction temperature-1Under conditions of carry out dehydrogenation reaction.
7 gas of table point mixing carbon four forms table
8 depropanization mixing carbon four of table forms table
| Mix four component of carbon | Content/wt% |
| Iso-butane | 44.80 |
| Normal butane | 49.47 |
| N-butene | 0.20 |
| Isobutene | 0.58 |
| Anti- butylene | 0.25 |
| Maleic | 0.40 |
| C5+ (contains isopentane) | 4.30 |
| It is total | 100.00 |
The mass yield of system each component in process are as follows: dry gas 2.76%, propylene 36.60%, propane 10.23%, MTBE
15.87%, alkylate oil 28.38%, aromatization carburetion 3.16%, wherein hydrogen accounts for 79.05vol% in dry gas.
Embodiment 4
The raw material of embodiment 4 is identical as the raw material of embodiment 1: catalytic cracking liquefied gas, that is, liquefied gas raw material 2 (logistics d),
Lighter hydrocarbons recovery liquefied gas and hydrogen recycling liquefied gas are mixed into (the logistics a) of liquefied gas raw material 1.Raw material composition is shown in Table 1, methanol (object
H) feedstock property is shown in Table 4 to stream.Process flow is same as Example 1 in embodiment 4.(logistics g) composition is shown in Table gas point mixing carbon four
9, (logistics c) composition is shown in Table 10 to depropanization mixing carbon four.Embodiment 4 is difference from example 1 is that the following aspects:
9 gas of table point mixing carbon four forms table
| Mix four component of carbon | Content/wt% |
| Iso-butane | 28.70 |
| Normal butane | 6.22 |
| N-butene | 13.80 |
| Isobutene | 20.80 |
| Anti- butylene | 14.80 |
| Maleic | 9.90 |
| C5+ (contains isopentane) | 5.78 |
| It is total | 28.70 |
10 depropanization mixing carbon four of table forms table
| Mix four component of carbon | Content/wt% |
| Iso-butane | 44.83 |
| Normal butane | 50.22 |
| N-butene | 0.17 |
| Isobutene | 0.44 |
| Anti- butylene | 0.14 |
| Maleic | 0.29 |
| C5+ (contains isopentane) | 3.90 |
| It is total | 100.00 |
1. 45 DEG C of etherification reaction temperature, reaction pressure 1.0MPa, under the conditions of alcohol hydrocarbon ratio is 0.5, carrying out etherification reaction.It urges
Changing catalyst loading pattern in destilling tower 3 is the filling structure mode in ZL201520508723.2 in embodiment 1, and catalyst is direct
In filling and filling component.In methanol extraction tower 4, (logistics j) feeding temperature is 42 DEG C to unreacted carbon four, and pressure is
1.0MPa, tower reactor are that ((content of methanol is the mixture of logistics m), water and methanol in logistics m) for the mixture of water and methanol
20.3%.
2. catalyst system is sulfuric acid in alkylation reactor 5, reaction feed temperature is 8 DEG C, reaction pressure 1.0MPa.It is different
Butane and butene alkylation, butene conversion are not less than 99%, and 6 tower top of alkylate knockout tower obtains tower top alkylation tail
Gas (logistics p), wherein butane content 68%.
3. aromatized catalyst uses the aromatisation prepared using the Catalyst Preparation Example 7 in patent CN1586721A
Catalyst SIHZSM-5 (A) -04 is 430 DEG C, reaction pressure 2.5MPa, air speed 2.0h in reaction temperature-1Under conditions of, into
Row aromatization.Aromatization products (logistics q) through aromatization products knockout tower 8 separation after obtain aromatization carburetion (logistics r) and
(logistics s), (propane content is 9.58% to aromatisation tail gas to aromatisation tail gas in logistics s).
4. catalytic dehydrogenation unit 10 uses fluidized-bed reactor, catalyst is microspherical catalyst.With Al2O3For carrier, load
Cr, Ni, Cu, Ca, Mg, K element, are prepared using infusion process, vector contg 84%, active component content 12%, auxiliary agent content
4%.It is 595 DEG C, reaction pressure 0.2MPa, air speed 2.0h in reaction temperature-1Under conditions of carry out dehydrogenation reaction.
The mass yield of system each component in process are as follows: dry gas 5.16%, propylene 36.47%, propane 17.30%, MTBE
10.47%, alkylate oil 24.26%, aromatization carburetion 6.35%, wherein hydrogen accounts for 82.32vol% in dry gas.
Above embodiments can be seen that the method for the present invention, except can be in addition to output certain proportion gasoline addO-on therapy, also by propane
Dehydrogenation produces propylene, improves the added value of propane, while by-product hydrogen.Remaining propane negligible amounts, can also be by product
In the propane cycles isolated to the further dehydrogenation of dehydrogenating propane device.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (19)
1. a kind of method using liquefied gas production high value added product, which is characterized in that process flow mainly includes depropanization
Unit, gas sub-unit, etherificate unit, alkylation, aromatisation unit, catalytic dehydrogenation unit, comprising the following steps:
(1) depropanization unit includes a depropanizing tower, and effect is that liquefied gas raw material 1 is separated into propane 1 and depropanization mixing carbon
Four；
(2) after liquefied gas raw material 2 is after the separation of gas sub-unit, 2 gentle points of propylene, propane mixing carbon four be can be obtained；
(3) gas point mixing carbon four is mixed with methanol, preheat, sent later to methyltertiarvbutyl ether reactor, etherification product is through urging after mixing
After changing destilling tower, unreacted carbon four and MTBE are obtained, unreacted carbon four enters methanol extraction tower, carries out by extractant of water
Methanol extraction obtains the mixture of carbon four and water and methanol after ether；
By step (1) in obtained depropanization mixing carbon four be divided into two streams, logistics c1 and logistics c2 in proportion, wherein
Logistics c1 is mixed with carbon four after ether, is sent jointly to alkylation reactor, under the effect of the catalyst, isobutane and butene into
Alkylate is sent into alkylate knockout tower, obtains alkylate oil and alkylation by row alkylated reaction after reaction
Tail gas；
By step (4) in logistics c2 with alkylation tail gas together with send to aromatization reactor, under the effect of the catalyst, fourth
Alkane carries out aromatization, after reaction send aromatization products to aromatization products knockout tower, obtains aromatization carburetion and virtue
Structure tail gas；
By step (1) obtained in propane 1 and step (2) obtained in propane 2 and step (5) obtained in aromatisation tail gas be total to
With sending to catalytic dehydrogenation unit, propane carries out dehydrogenation reaction under the effect of the catalyst, and propylene by-product hydrogen simultaneously can be obtained；
Wherein: the sum of 1 iso-butane of liquefied gas raw material and normal butane are not less than 40%, preferably not below 45%.In liquefied gas raw material 2
Isobutene content is not less than 10%, preferably not below 11%, and iso-butane content is not less than 13%, preferably not below 15%.
2. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that liquefied gas is former
Material 1 is lighter hydrocarbons liquefied gas, hydrogen recycles one or both of liquefied gas.
3. the method according to claim 2 using liquefied gas production high value added product, which is characterized in that lighter hydrocarbons liquefaction
Gas are as follows: isomerization dry gas, diesel oil hydrogenation stripping tower overhead gas, is hydrocracked stripping tower overhead gas, stone brain at residual hydrogenation stripping tower overhead gas
Oily hydrogenation reaction product is hydrocracked stripping liquid of top of the tower, is hydrocracked fractionation liquid of top of the tower, reforms one or more of liquefied gas
The product that is obtained through light ends unit of mixture.
4. the method according to claim 2 using liquefied gas production high value added product, which is characterized in that hydrogen recycling
Liquefied gas is with catalysis drying gas, raffinates oil that one such or two kinds are liquefied gas of the raw material through hydrogen gas recovering device output.
5. the method according to claim 2 using liquefied gas production high value added product, which is characterized in that lighter hydrocarbons liquefaction
Iso-butane content is not less than 25%, preferably not below 30% in gas；Normal butane content is not less than 30%, preferably not below 35%.
6. the method according to claim 2 using liquefied gas production high value added product, which is characterized in that hydrogen recycling
Iso-butane content is not less than 28%, preferably not below 30% in liquefied gas；Normal butane content is not less than 12%, preferably not below
15%.
7. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that liquefied gas is former
Material 2 is catalytic cracking liquefied gas.
8. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that the logistics
C1 accounts for the 25~35% of the gross mass of depropanization mixing carbon four, and preferably 27~30%.
9. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that etherification reaction
Device uses fixed bed reactors, and the number of fixed bed reactors is one or two.
10. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that etherificate is anti-
10~80 DEG C of temperature, preferably 25~50 DEG C are answered, reaction pressure is 0.01~3.0MPa, preferably 0.05~1.5MPa, methanol
Mass ratio with hydrocarbon feed is 0.1~1.0, preferably 0.15~0.5.
11. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that methanol extraction
It takes methanol content in the mixture for the water and methanol that tower obtains to be not higher than 30%, is preferably not higher than 25%.
12. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that extraction tower
Feeding temperature is 20~70 DEG C, and preferably 30~60 DEG C, pressure is 0.1~2.0MPa, preferably 0.5~1.5MPa.
13. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that alkylation
Catalyst in reactor is liquid acid catalyst, preferably sulfuric acid or hydrofluoric acid.
14. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that alkylation
Reaction temperature is 0.1~20 DEG C, and preferably 2~10 DEG C, reaction pressure is 0~10MPa, preferably 0.5~2.0MPa.
15. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that aromatisation
Catalyst in reactor is molecular sieve catalyst, preferably ZSM-5 or metal-modified HZSM-5 molecular sieve catalyst.
16. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that aromatisation
Reaction temperature is 300~600 DEG C, preferably 350~550 DEG C；0.05~4.0MPa of reaction pressure, preferably 0.08~4.0MPa；Liquid
When air speed 0.01~10h-1, preferably 0.05~5h-1。
17. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that catalysis is de-
The catalyst used in hydrogen reactor is platinum group or chromium-based catalysts.
18. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that catalysis is de-
The reactor of hydrogen unit is fixed bed reactors or fluidized-bed reactor.
19. the method according to claim 1 using liquefied gas production high value added product, which is characterized in that dehydrogenation is urged
Agent is with Al2O3For carrier, the active component of load is one or more of Pt, Cr, Mo, V element, the auxiliary agent of load be Ni,
One or more of Cu, Ca, Mg, K element；Vector contg 50~90%, active component constituent content 1~40%, auxiliary agent member
Cellulose content 0.1~30%.
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| CN101935265A (en) * | 2009-06-29 | 2011-01-05 | 上海傲佳能源科技有限公司 | Liquefied gas catalytic pyrolysis process |
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| CN103739454A (en) * | 2013-12-24 | 2014-04-23 | 山东滨州裕华化工厂有限公司 | Process for preparing MTBE (Methyl Tert Butyl Ether) from C4 fraction in etherified liquefied gas |
| CN106433772A (en) * | 2016-11-15 | 2017-02-22 | 宁夏宝塔石化科技实业发展有限公司 | Method for pre-treating raw materials of etherified C4 and naphtha aromatization |
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| US4484013A (en) * | 1983-12-30 | 1984-11-20 | Uop Inc. | Process for coproduction of isopropanol and tertiary butyl alcohol |
| US4544777A (en) * | 1984-10-24 | 1985-10-01 | Phillips Petroleum Company | Combination alkylation-etherification process |
| CN101935265A (en) * | 2009-06-29 | 2011-01-05 | 上海傲佳能源科技有限公司 | Liquefied gas catalytic pyrolysis process |
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