CN115247079B - Method for increasing yield of ethylene cracking raw material - Google Patents
Method for increasing yield of ethylene cracking raw material Download PDFInfo
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- CN115247079B CN115247079B CN202110461308.6A CN202110461308A CN115247079B CN 115247079 B CN115247079 B CN 115247079B CN 202110461308 A CN202110461308 A CN 202110461308A CN 115247079 B CN115247079 B CN 115247079B
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- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000005336 cracking Methods 0.000 title claims abstract description 39
- 239000002994 raw material Substances 0.000 title claims abstract description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000005977 Ethylene Substances 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 33
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 230000008020 evaporation Effects 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 8
- 231100000572 poisoning Toxicity 0.000 claims abstract description 6
- 230000000607 poisoning effect Effects 0.000 claims abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 86
- 239000002808 molecular sieve Substances 0.000 claims description 59
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 56
- 238000004073 vulcanization Methods 0.000 claims description 51
- 238000001035 drying Methods 0.000 claims description 47
- 239000000047 product Substances 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000012071 phase Substances 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 27
- 239000012298 atmosphere Substances 0.000 claims description 24
- 239000007791 liquid phase Substances 0.000 claims description 21
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 21
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017318 Mo—Ni Inorganic materials 0.000 claims description 3
- -1 VIB metals Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000004611 spectroscopical analysis Methods 0.000 claims description 3
- 229910017313 Mo—Co Inorganic materials 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical group S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims 2
- 238000011065 in-situ storage Methods 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 abstract description 27
- 239000000243 solution Substances 0.000 description 28
- 239000003921 oil Substances 0.000 description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 23
- 229920002472 Starch Polymers 0.000 description 23
- 229910017604 nitric acid Inorganic materials 0.000 description 23
- 239000008107 starch Substances 0.000 description 23
- 235000019698 starch Nutrition 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 239000000843 powder Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 11
- 238000004898 kneading Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000005486 sulfidation Methods 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003568 thioethers Chemical class 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2400/04—Diesel oil
-
- 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
Abstract
The method for increasing yield of ethylene cracking raw materials adopts a fixed bed reactor with a special structure, wherein the inside of the fixed bed reactor is sequentially divided into a gas phase reaction zone, a flash evaporation zone and a gas-liquid countercurrent reaction zone from top to bottom, oil products enter from the flash evaporation zone, hydrogen is introduced from the bottom of the reactor, a gas phase hydrogenation product outlet is arranged at the top of the gas phase reaction zone, and a heavy phase hydrogenation product outlet is arranged at the bottom of the gas-liquid countercurrent reaction zone; the hydrocracking catalyst with high cracking performance and high nitrogen poisoning resistance is filled in the gas-liquid countercurrent reaction zone, and is a special catalyst. The ethylene cracking raw material is increased in yield by the cooperation of the reactor with a special structure and the catalyst, and the obtained heavy fraction hydrogenation product can be used as the raw material to further co-produce high-quality diesel blending components of ultralow sulfur and low polycyclic aromatic hydrocarbon. The method has great flexibility, and meets the market demand for the diesel oil product and the ethylene cracking raw material by adjusting the proportion of the ethylene cracking raw material and the diesel oil product.
Description
Technical Field
The invention belongs to the field of clean oil refining, and particularly relates to a method for producing an ethylene cracking raw material.
Background
Along with the contradiction of surplus diesel oil productivity and shortage of chemical raw materials in China, more and more oil refining enterprises start to transform to chemical industry. In order to meet the requirements of refineries for reducing diesel oil yield and increasing ethylene cracking raw materials, development of related technologies is urgently needed. Currently, in order to reduce the diesel oil yield and increase the ethylene cracking feedstock, the hydrocracking technology is mainly used, but the energy consumption and the hydrogen consumption of the technology are large, and the cost of oil refining enterprises is increased. In addition, in order to further reduce the environmental pollution of diesel fuel, the polycyclic aromatic hydrocarbon content in diesel fuel needs to be further reduced.
CN201210357165.5 discloses a diesel hydrofining method comprising injecting hydrogen into diesel, and contacting with a catalyst having a catalytic hydrogenation effect in a hydrogenation reactor under liquid phase hydrotreating conditions, wherein hydrogen is injected into the diesel once or in several times through holes having a pore size of nanometer size. According to the diesel hydrofining method of the present invention, hydrogen is injected into diesel through the through holes having an average pore diameter of nano-size, and hydrogen can be highly dispersed and rapidly dissolved in diesel even without the aid of a diluent or a circulating oil. Furthermore, the method of the invention can obtain good hydrofining effect when being used for hydrofining diesel oil, the sulfur content in the obtained refined oil can be below 50 mug/g, the nitrogen content can be below 15 mug/g, and the obtained refined oil has higher cetane number. However, the method cannot further reduce the sulfur content, the nitrogen content and the polycyclic aromatic hydrocarbon content in the diesel oil by the method under the influence of the hydrogen dissolution amount, the temperature and the hydrogen partial pressure, and cannot meet the quality standard of the diesel oil in China III.
CN201310540464.7 discloses a catalytic cracking diesel hydro-conversion method. After the catalytic diesel oil is mixed with hydrogen, a hydrofining reactor is first used for hydrofining reaction; the effluent of the hydrofining reaction directly enters a hydrocracking reactor to contact and react with a graded catalyst bed in the hydrocracking reactor; at least two cracking catalyst beds are arranged in the hydrocracking reactor, and the hydrogenation activity of the hydrocracking catalyst is reduced according to the flow direction of reaction materials; and separating and fractionating the hydrocracking reaction effluent to obtain naphtha and diesel oil. The hydrofining product directly enters a hydrocracking reactor, wherein the hydrofining product contains a large amount of impurities such as hydrogen sulfide, ammonia gas and the like, and on one hand, the hydrofining product occupies the active site of a hydrocracking catalyst, and on the other hand, the hydrofining product can cause molecular sieve poisoning in the hydrocracking catalyst; in addition, hydrocracking products (comprising light and heavy components) need to pass through the entire catalyst bed, still causing excessive cracking and secondary cracking. It can be seen that although the invention can produce ethylene cracking raw material and diesel oil products, the energy consumption is large, the hydrogen consumption is large, and the product yield is low.
CN200910012491.0 discloses a combined hydrogenation method for gasoline and diesel, in which gasoline raw material is mixed with hydrogen, and passed through a first reaction zone under the condition of gasoline hydrofining, the first reaction zone uses hydrofining catalyst, and the gasoline raw material is coker gasoline and/or catalytic gasoline; mixing the reaction effluent of the first reaction zone with a diesel oil raw material, and passing through a second reaction zone under the condition of diesel oil hydrodearomatization, wherein the second reaction zone uses a hydrofining catalyst, and the diesel oil raw material is one or more of straight-run diesel oil, coked diesel oil or catalytic cracking diesel oil; the reaction effluent from the second reaction zone passes through a third reaction zone under the condition of diesel hydrodesulfurization, wherein the third reaction zone uses a hydrodesulfurization catalyst. The method effectively utilizes the heat released during the hydrogenation of the secondary processed gasoline, has simple process and low energy consumption, and can obtain high-quality gasoline and diesel products. However, the gasoline component of the method can further carry out hydrogenation reaction through the second reaction zone and the third reaction zone, so that the active sites of the hydrodearomatization and hydrodesulfurization reactions of the diesel are occupied, and the activity of the hydrodearomatization and hydrodesulfurization reactions of the diesel is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for increasing the yield of ethylene cracking raw materials, which adopts the cooperation of a special catalyst and a process flow, and can realize the yield increase of high-quality ethylene cracking raw materials under the conditions of simple flow, low energy consumption and low cost, especially by taking inferior diesel oil mixed oil as the raw material.
The method for increasing the yield of the ethylene cracking raw material adopts a reactor with the following structure:
the reactor is a fixed bed reactor, an oil product raw material inlet is arranged at the middle section of the fixed bed reactor, the raw material inlet is connected with a flash evaporation zone, the upper part of the flash evaporation zone is a gas phase reaction zone, the lower part of the flash evaporation zone is a gas-liquid countercurrent reaction zone, the bottom of the fixed bed reactor is provided with a hydrogen inlet, the top of the gas phase reaction zone is provided with a gas phase hydrogenation product outlet, and the bottom of the gas-liquid countercurrent reaction zone is provided with a heavy phase hydrogenation product outlet; the hydrocracking catalyst with high cracking performance and high nitrogen poisoning resistance is filled in the gas-liquid countercurrent reaction zone, and comprises a carrier and an active component, wherein the carrier is a mixture of a molecular sieve and alumina, and the molecular sieve accounts for 5-25wt%, preferably 8-20wt% based on the total weight of the carrier; the active components are VIB metal sulfide and VIII metal oxide, the VIB metal sulfide is 2-30%, preferably 15-28% and the VIII metal oxide is 2-10%, preferably 4-8% based on the total weight of the catalyst, the VIB metal sulfide is loaded on a molecular sieve, and the VIII metal oxide is loaded on the molecular sieve and alumina;
the method for increasing the yield of the ethylene cracking raw material comprises the following steps: the oil product is sent into a flash evaporation zone of a fixed bed reactor, the oil product is separated into a liquid phase component and a gas phase component after flash evaporation, the gas phase component upwards enters a gas phase reaction zone to carry out hydrogenation and olefin removal reaction, and a reaction product is discharged from a gas phase hydrogenation product outlet at the top of the reactor; the liquid phase component after flash evaporation enters a gas-liquid countercurrent reaction zone downwards, hydrodesulfurization, denitrification and cracking reactions are carried out under the action of a filled hydrocracking catalyst, the light component obtained by the cracking reaction enters a gas phase reaction zone upwards for hydrodeolefination reaction, and the heavy component obtained by the cracking reaction flows out as a product from a heavy phase hydrogenation product outlet.
Furthermore, because the hydrogen enters from the bottom of the reactor, the hydrogen is contacted and reacted with the liquid phase component after flash evaporation to cause the liquid phase component to undergo hydrocracking, and the obtained heavy phase hydrogenation product has more dissolved hydrogen, the method further comprises the process of liquid phase hydrogenation of the heavy phase hydrogenation product so as to further co-produce the high-quality diesel blending component of ultralow sulfur and low polycyclic aromatic hydrocarbon. The liquid phase hydrogenation may be performed using a general liquid phase hydrogenation catalyst, preferably a nickel-based hydrogenation catalyst, and hydrogen may be added as needed.
Further, the hydrocracking catalyst (oxidation state) has a molar ratio of +4 valent group VIB metal to the total amount of group VIB metal of 60% -90%, preferably 70% -90%, more preferably 80% -90%, and most preferably 80% -86% when analyzed by XPS spectroscopy. The oxidation state herein mainly means that the group VIII metal is not sulfided but exists in an oxidized state.
Further, when the hydrogenation catalyst (in a vulcanized state) is analyzed by XPS energy spectrum, the mole ratio of the +4 valence state of the VIB metal to the total amount of the VIB metal is 65-100%. The sulfidation state herein mainly means the conversion of the group VIII metal into the sulfidation state.
Further, the VIB group metal sulfide is molybdenum sulfide or/and tungsten sulfide, and the VIII group metal oxide is nickel oxide or/and cobalt oxide. The molecular sieve is at least one selected from a Y-type molecular sieve, a ZSM-5 molecular sieve, a beta-type molecular sieve and an MCM-41 molecular sieve.
Furthermore, the hydrocracking catalyst is a semi-sulfided catalyst, in-reactor pre-sulfidation is not needed during use, sulfide in raw oil can sulfide the VIII group metal oxide easy to sulfide in the catalyst, the hydrogenation activity of the catalyst is gradually improved, the excessive temperature rise caused by the excessive activity of the catalyst in the initial stage of reaction is prevented, and meanwhile, the operation risk is reduced without in-reactor sulfidation.
Further, the hydrocracking catalyst is prepared by the following method:
(1) Impregnating a molecular sieve with impregnating solution containing VIB group metal, and carrying out ultrasonic treatment, drying, roasting and vulcanization treatment to obtain a modified molecular sieve;
(2) Mixing the modified molecular sieve in the step (1), alumina, a peptizing agent and an extrusion aid, extruding to form strips, and drying and roasting in an inert atmosphere to obtain a modified alumina carrier;
(3) Impregnating the modified alumina carrier in the step (2) with an impregnating solution containing a group VIII metal, and then drying and roasting in an inert atmosphere to obtain the hydrocracking catalyst.
Further, the impregnating solution of the group VIB metal in the step (1) is a phosphate or ammonium salt solution of the group VIB metal, and the preparation method thereof is well known to those skilled in the art, and an isovolumetric impregnation or supersaturation impregnation mode is adopted. The group VIB metal is preferably Mo and/or W.
Further, the ultrasonic conditions of step (1) are: sonicating at room temperature for 1-3 hours. The drying conditions are as follows: drying at 90-200deg.C for 3-6 hr; the roasting conditions are as follows: roasting temperature is 300-500 ℃ and roasting time is 2-6 hours.
Further, the vulcanization treatment in the step (1) is dry vulcanization or wet vulcanization. The dry vulcanizing agent is hydrogen sulfide, and the wet vulcanizing agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12h.
Further, the peptizing agent in the step (2) is at least one of nitric acid, phosphoric acid or acetic acid, and the extrusion assisting agent is one or two of starch and polyethylene glycol. The inert atmosphere is N 2 And one or more of inert gases; the drying temperature of the step (2) is 20-90 ℃ and the drying time is 4-16 hours; the roasting temperature is 500-800 ℃ and the roasting time is 2-5 hours.
Further, the impregnating solution of the group VIII metal in the step (3) is a nitrate, acetate or sulfate solution of the group VIII metal, etc., and an equal volume impregnation mode may be adopted, where the group VIII metal is Ni and/or Co. The inert atmosphere is N 2 And one or more of inert gases; the drying temperature of the step (3) is 20-90 ℃ and the drying time is 4-16 hours; the roasting temperature is 200-400 ℃ and the roasting time is 2-5 hours.
In the method, the prepared hydrocracking catalyst is acted with the molecular sieve firstly, sulfide of the hydrocracking catalyst is wrapped on the surface of the molecular sieve, so that the contact between nitride and the molecular sieve in the reaction process can be blocked, meanwhile, the nitride in the raw material can firstly perform hydrodenitrogenation reaction with the sulfide of the VIB group metal on the surface of the molecular sieve, so that the molecular sieve is protected, nitrogen poisoning of the molecular sieve is prevented, and the hydrogenolysis activity and the chain breakage activity of the catalyst are improved, so that the yield of naphtha is improved;
further, in the method, the oil product raw material is diesel oil, and is selected from one or more of straight-run diesel oil, catalytic cracking diesel oil, coker diesel oil and ebullated bed residual oil hydrogenated diesel oil; the distillation range is 200-450 ℃, the sulfur content is not more than 16000 mug/g, the nitrogen content is not more than 1200 mug/g, and the cetane number is not less than 37.
Further, in the above method, the flash evaporation zone is used for separating light fraction below 240 ℃ from the raw material, the light fraction enters the gas phase reaction zone as a gas phase component, and the heavy fraction above 240 ℃ enters the gas-liquid countercurrent reaction zone as a liquid phase component.
Furthermore, in the method, the gas phase reaction zone is used for the hydrogenation and olefin removal reaction of gas phase components (light fraction), and the gas phase reaction zone is filled with Mo-Ni and/or Mo-Co type light fraction oil hydrogenation catalyst, such as FH-40 series light fraction oil hydrogenation special catalyst developed by FRIPP. The light distillate hydrogenation catalyst does not need to be presulfided in a reactor before use. The process conditions of the gas phase reaction zone are as follows: the pressure is 1.0-10.0 MPa, preferably 2.0-6.0 MPa, wherein the hydrogen partial pressure accounts for 50% -70% of the total pressure ratio; volume space velocity is 0.1-12.0 h -1 Preferably 1.0 to 8.0 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding temperature is 130-300 ℃, preferably 180-300 ℃; hydrogen oil volume ratio 10: 1-1000: 1, preferably 100: 1-800: 1.
in the method of the invention, the gas-liquid countercurrent reaction zone is used for deep desulfurization, denitrification and hydrocracking of liquid phase components (heavy fractions). The process conditions are as follows: the pressure is 1.0-12.0 MPa, preferably 5.0-10.0 MPa, wherein the hydrogen partial pressure accounts for 60% -90% of the total pressure ratio; volume space velocity is 0.1-10.0 h -1 Preferably 1.0 to 3.0 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 220-450 ℃, preferably 350-380 ℃; hydrogen oil volume ratio 10: 1-1000: 1, preferably 100: 1-800: 1.
the invention has the following advantages:
(1) Compared with the existing diesel hydrogenation technology, the method can realize the increase of ethylene cracking raw materials, and the obtained heavy fraction hydrogenation product can be used as raw materials to further coproduce high-quality diesel blending components of ultralow sulfur and low polycyclic aromatic hydrocarbon.
(2) After the raw oil enters the flash evaporation zone, gas phase components (light fraction) enter the gas phase reaction zone, mercaptan and thioether in the light fraction oil can vulcanize the catalyst, so that the olefin saturation property of the catalyst is slowly improved, and the problem that the reaction temperature is rapidly increased due to the overhigh olefin hydrogenation activity of the catalyst, so that the olefin is coked on the surface of the catalyst is solved.
(3) The liquid phase components (heavy fractions) after the flash evaporation zone enter a gas-liquid countercurrent reaction zone, and the ascending hydrogen can timely bring naphtha generated by the reaction to the gas-phase reaction zone, so that excessive cracking and secondary cracking of the naphtha are prevented, and meanwhile, heat generated by the reaction can be taken away, and the coking reaction of macromolecular compounds such as polycyclic aromatic hydrocarbon and the like on the catalyst is prevented under a high-temperature environment.
(4) The special hydrocracking catalyst is filled in the gas-liquid countercurrent reaction zone, has special properties, and the VIB group metal sulfide is wrapped on the surface of the molecular sieve, so that the contact between nitride and the molecular sieve in the reaction process can be blocked, meanwhile, the nitride in the raw material can firstly perform hydrodenitrogenation reaction with the VIB group metal sulfide on the surface of the molecular sieve, the molecular sieve is protected, and the nitrogen poisoning of the molecular sieve is prevented, so that the hydrogenolysis activity and the chain breakage activity of the catalyst are improved, and the yield of naphtha is further improved.
(5) In addition, the hydrocracking catalyst does not need to be vulcanized, the metal oxide which is difficult to be vulcanized is vulcanized in advance, and the metal oxide which is easy to be vulcanized in the semi-vulcanized catalyst can be gradually vulcanized along with the hydrogen sulfide generated by the reaction product, so that the temperature flying caused by the over-high initial activity of the reaction can be weakened, and the coking reaction can be prevented; because the light distillate hydrogenation catalyst filled in the gas phase reaction zone does not need to be vulcanized, the whole reaction system can omit the process of presulfiding in the reactor.
(6) Because the macromolecule sulfur-containing compound and the nitrogenous compound need to be firstly hydrogenated and then removed, liquid phase hydrogenation is directly carried out, and competing reaction is formed between the macromolecule sulfur-containing compound and the nitrogenous compound and the polycyclic aromatic hydrocarbon hydrogenation saturation.
(7) The method can flexibly adjust the proportion of the ethylene cracking raw material and the diesel oil product by adjusting different process conditions, thereby meeting the requirements of the market on the diesel oil product and the ethylene cracking raw material.
Drawings
FIG. 1 is a schematic diagram of a reactor used in the method for increasing yield of ethylene cracking feedstock according to the present invention.
In the figure: 1. the method comprises the following steps of oil raw materials, namely 2 parts of hydrogen, 3 parts of gas phase reaction zone, 4 parts of flash evaporation zone, 5 parts of gas-liquid countercurrent reaction zone, 6 parts of gas phase hydrogenation product and 7 parts of heavy phase hydrogenation product.
Detailed Description
The invention will now be described in more detail with reference to the accompanying drawings and examples, which are not intended to limit the invention thereto.
The composition of the catalyst provided by the invention can be characterized by combining inductively coupled plasma ICP and XPS energy spectrum, wherein the total content of VIB group metal and the total content of VIII group metal in the catalyst are firstly characterized by ICP, and then the content of metal elements with different valence states in the catalyst is quantitatively characterized by an XPS energy spectrum. The catalyst provided by the invention has metal sulfidation degree, mo is used 4+ Or W 4+ The content indicates the degree of metal sulfidation of the catalyst. The mixture was treated with 30mL/min H at 320 ℃ 2 S is vulcanized for 2 hours, XPS spectrometer is used for characterizing the metal valence state of the surface of the sample, XPS PEAK version4.0 is adopted for respectively carrying out fitting peak separation on Mo3d, W4f, co2p and Ni2p energy spectrums, and the metal vulcanization degree is obtained according to the peak area calculation.
In examples 1-8, the hydrocracking catalyst used in the gas-liquid countercurrent reaction zone was first prepared:
example 1
(1) The ammonium heptamolybdate solution was impregnated into the beta-type molecular sieve, then sonicated at room temperature for 2 hours, then dried at 110℃for 3 hours, calcined at 400℃for 6 hours, then calcined with a solution containing 1.5% H 2 S, carrying out vulcanization treatment on hydrogen at the vulcanization temperature of 340 ℃, the vulcanization pressure of 5.4MPa and the vulcanization time of 3h, and then carrying out vulcanization treatment on the hydrogen in N 2 And cooling to room temperature in the atmosphere to obtain the modified molecular sieve.
(2) Uniformly mixing the modified molecular sieve prepared in the step (1) with alumina powder, nitric acid, starch and deionized water, wherein the modified molecular sieve is prepared by the following steps: alumina powder: nitric acid: starch: the mass ratio of deionized water is 8:92:4:3:60, then kneading, extruding and molding, then in N 2 Drying at 60 ℃ for 10 hours in the atmosphere, and roasting at 600 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the beta-type molecular sieve is 8%.
(3) And (3) immersing cobalt nitrate solution in an equal volume into the modified alumina carrier prepared in the step (2), drying at 60 ℃ for 4 hours in a nitrogen atmosphere, and roasting at 250 ℃ for 3 hours to obtain the catalyst C-1.
The catalyst C-1 comprises the following components in percentage by weight: moS (MoS) 2 18% cobalt oxide 4.4% and the rest is carrier.
Example 2
(1) Immersing an ammonium heptamolybdate solution in a beta-type molecular sieve, then sonicating at room temperature for 3 hours, then drying at 110 ℃ for 3 hours, calcining at 350 ℃ for 4 hours, then using a solution containing 1.5% H 2 S, carrying out vulcanization treatment on hydrogen at the vulcanization temperature of 360 ℃, the vulcanization pressure of 3.4MPa and the vulcanization time of 4h, and then carrying out vulcanization treatment on the hydrogen in N 2 And cooling to room temperature in the atmosphere to obtain the modified molecular sieve.
(2) Uniformly mixing the modified molecular sieve prepared in the step (1) with alumina powder, nitric acid, starch and deionized water, wherein the modified molecular sieve is prepared by the following steps: alumina powder: nitric acid: starch: the mass ratio of deionized water is 12:88:4:3:50, then kneading, extruding and molding, then in N 2 Drying for 4 hours at 90 ℃ in the atmosphere, and roasting for 3 hours at 600 ℃ to obtain the modified alumina carrier, wherein the content of the beta-type molecular sieve is 12%.
(3) And (3) immersing nickel nitrate solution in an equal volume into the modified alumina carrier prepared in the step (2), and then drying at 60 ℃ for 3 hours and roasting at 260 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-2.
The catalyst C-2 comprises the following components in percentage by weight: moS (MoS) 2 20 percent of nickel oxide, 5.0 percent of nickel oxide and the balance of carrier.
Example 3
(1) Immersing the beta-type molecular sieve in ammonium metatungstate solution, ultrasonic treating at room temp for 3 hr, drying at 130 deg.C for 5 hr, baking at 350 deg.C for 3 hr, and adding H (1.5%) 2 S, hydrogen is vulcanized, the vulcanization temperature is 340 ℃, the vulcanization pressure is 4.0MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the modified molecular sieve.
(2) Taking the modified molecular sieve and alumina powder prepared in the step (1)Uniformly mixing nitric acid, starch and deionized water, wherein the modified molecular sieve is prepared by the following steps of: alumina powder: nitric acid: starch: the mass ratio of deionized water is 16:84:4:3:50, then kneading, extruding and molding, then in N 2 Drying at 90 ℃ for 5 hours in the atmosphere, and roasting at 600 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the beta-type molecular sieve is 16%.
(3) And (3) immersing nickel nitrate solution in an equal volume into the modified alumina carrier prepared in the step (2), and then drying at 80 ℃ for 3 hours and roasting at 250 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-3.
The catalyst C-3 comprises the following components in percentage by weight: WS (WS) 2 18% nickel oxide 6.0% and the rest is carrier.
Example 4
(1) Immersing the beta-type molecular sieve in the solution of ammonium heptamolybdate and ammonium metatungstate, ultrasonic treating at room temp for 3 hr, drying at 120 deg.C for 6 hr, calcining at 350 deg.C for 3 hr, and adding H (1.5 wt.%) 2 S, hydrogen is vulcanized, the vulcanization temperature is 340 ℃, the vulcanization pressure is 5.4MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the modified molecular sieve.
(2) Uniformly mixing the modified molecular sieve prepared in the step (1) with alumina powder, nitric acid, starch and deionized water, wherein the modified molecular sieve is prepared by the following steps: alumina powder: nitric acid: starch: the mass ratio of deionized water is 19:81:4:3:45, then kneading, extruding and molding, and then in N 2 Drying at 80 ℃ for 10 hours in the atmosphere, and roasting at 700 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the beta-type molecular sieve is 19%.
(3) And (3) immersing nickel nitrate solution in an equal volume into the modified alumina carrier prepared in the step (2), and then drying at 70 ℃ for 3 hours and roasting at 300 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-4.
The catalyst C-4 comprises the following components in percentage by weight: moS (MoS) 2 10%, WS 2 10 percent of nickel oxide, 6.3 percent of nickel oxide and the balance of carrier.
Example 5
(1) Impregnating an ammonium heptamolybdate solution into a ZSM-5 molecular sieveThen sonicated at room temperature for 3 hours, then dried at 130℃for 4 hours, calcined at 420℃for 3 hours, then treated with a solution containing 1.5% H 2 S, carrying out vulcanization treatment on hydrogen at the vulcanization temperature of 360 ℃, the vulcanization pressure of 3.6MPa and the vulcanization time of 4h, and then carrying out vulcanization treatment on the hydrogen in N 2 And cooling to room temperature in the atmosphere to obtain the modified molecular sieve.
(2) Uniformly mixing the modified molecular sieve prepared in the step (1) with alumina powder, nitric acid, starch and deionized water, wherein the modified molecular sieve is prepared by the following steps: alumina powder: nitric acid: starch: the mass ratio of deionized water is 15:85:4:3:55, then kneading, extruding and molding, then in N 2 Drying at 90 ℃ for 5 hours in the atmosphere, and roasting at 550 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the ZSM-5 molecular sieve is 15%.
(3) And (3) immersing nickel nitrate solution in an equal volume into the modified alumina carrier prepared in the step (2), and then drying at 80 ℃ for 3 hours and roasting at 200 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-5.
The catalyst C-5 comprises the following components in percentage by weight: moS (MoS) 2 22 percent of nickel oxide, 6.0 percent of nickel oxide and the balance of carrier.
Example 6
(1) Immersing ammonium metatungstate solution in Y-type molecular sieve, ultrasonic treating at room temp for 3 hr, drying at 130 deg.C for 6 hr, calcining at 350 deg.C for 5 hr, and adding H (1.5%) 2 S, hydrogen is vulcanized, the vulcanization temperature is 300 ℃, the vulcanization pressure is 5.0MPa, the vulcanization time is 4h, and then the vulcanization is carried out on N 2 And cooling to room temperature in the atmosphere to obtain the modified molecular sieve.
(2) Uniformly mixing the modified molecular sieve prepared in the step (1) with alumina powder, nitric acid, starch and deionized water, wherein the modified molecular sieve is prepared by the following steps: alumina powder: nitric acid: starch: the mass ratio of deionized water is 18:82:4:3:55, then kneading, extruding and molding, then in N 2 Drying at 80 ℃ for 10 hours in the atmosphere, and roasting at 550 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the Y-type molecular sieve is 18 percent.
(3) And (3) immersing nickel nitrate solution in an equal volume into the modified alumina carrier prepared in the step (2), and then drying at 60 ℃ for 3 hours and roasting at 250 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-6.
The catalyst C-6 comprises the following components in percentage by weight: WS (WS) 2 22 percent of nickel oxide, 6.0 percent of nickel oxide and the balance of carrier.
Example 7
(1) Immersing the MCM-41 molecular sieve in ammonium meta-tungstate solution, ultrasonic treating at room temp for 3 hr, drying at 150 deg.C for 3 hr, calcining at 450 deg.C for 3 hr, and adding H (1.5%) 2 S, carrying out vulcanization treatment on hydrogen at the vulcanization temperature of 340 ℃, the vulcanization pressure of 4.0MPa and the vulcanization time of 2h, and then carrying out vulcanization treatment on the hydrogen in N 2 And cooling to room temperature in the atmosphere to obtain the modified molecular sieve.
(2) Uniformly mixing the modified molecular sieve prepared in the step (1) with alumina powder, nitric acid, starch and deionized water, wherein the modified molecular sieve is prepared by the following steps: alumina powder: nitric acid: starch: the mass ratio of deionized water is 15:85:4:3:55, then kneading, extruding and molding, then in N 2 Drying at 60 ℃ for 10 hours in the atmosphere, and roasting at 650 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the MCM-41 molecular sieve is 15%.
(3) And (3) immersing nickel nitrate solution in an equal volume into the modified alumina carrier prepared in the step (2), drying at 70 ℃ for 4 hours in a nitrogen atmosphere, and roasting at 250 ℃ for 3 hours to obtain the catalyst C-7.
The catalyst C-7 comprises the following components in percentage by weight: WS (WS) 2 20 percent of nickel oxide, 7.0 percent of nickel oxide and the balance of carrier.
Example 8
(1) Immersing ammonium metatungstate solution in the mixture of Y-type and beta-type molecular sieves, ultrasonic treating at room temp for 3 hr, drying at 120 deg.C for 3 hr, calcining at 450 deg.C for 3 hr, and adding H (1.5%) to it 2 S, carrying out vulcanization treatment on hydrogen at the vulcanization temperature of 360 ℃, the vulcanization pressure of 3.6MPa and the vulcanization time of 3h, and then carrying out vulcanization treatment on the hydrogen in N 2 And cooling to room temperature in the atmosphere to obtain the modified molecular sieve.
(2) Uniformly mixing the modified molecular sieve prepared in the step (1) with alumina powder, nitric acid, starch and deionized water, wherein the modification is carried outSub-sieve: alumina powder: nitric acid: starch: the mass ratio of deionized water is 25:75:4:3:55, then kneading, extruding and molding, then in N 2 Drying at 80 ℃ for 5 hours in the atmosphere, and roasting at 550 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the Y-type molecular sieve is 10 percent, and the content of the beta-type molecular sieve is 15 percent.
(3) And (3) immersing nickel nitrate solution in an equal volume into the modified alumina carrier prepared in the step (2), and then drying for 3 hours at 90 ℃ and roasting for 3 hours at 250 ℃ in a nitrogen atmosphere to obtain the catalyst C-8.
The catalyst C-8 comprises the following components in percentage by weight: WS (WS) 2 20 percent of nickel oxide, 6.0 percent of nickel oxide and the balance of carrier.
Comparative example 1
(1) Uniformly mixing a Y-type molecular sieve with alumina powder, nitric acid, starch and deionized water, wherein the Y-type molecular sieve is as follows: alumina powder: nitric acid: starch: the mass ratio of deionized water is 15:75:4:3:60, then kneading and extruding strips for molding, then drying at 80 ℃ for 5 hours, and roasting at 650 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the Y-type molecular sieve is 15%.
(2) Impregnating the ammonium metatungstate solution into the modified alumina carrier prepared in the step (1), and then adopting a catalyst containing 1.5% of H 2 S, carrying out vulcanization treatment on hydrogen at the vulcanization temperature of 360 ℃, the vulcanization pressure of 5.0MPa and the vulcanization time of 3h, and then carrying out vulcanization treatment on the hydrogen in N 2 And cooling to room temperature in the atmosphere to obtain the catalyst precursor.
(3) And (3) immersing nickel nitrate solution in an equal volume into the catalyst precursor prepared in the step (2), and then drying at 70 ℃ for 3 hours and roasting at 250 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst DC-1.
The catalyst DC-1 comprises the following components in percentage by weight: WS (WS) 2 20 percent of nickel oxide, 6.0 percent of nickel oxide and the balance of carrier.
Comparative example 2
(1) Uniformly mixing a Y-type molecular sieve with alumina powder, nitric acid, starch and deionized water, wherein the Y-type molecular sieve is as follows: alumina powder: nitric acid: starch: the mass ratio of deionized water is 15:75:4:3:60, then kneading and extruding strips for molding, then drying at 130 ℃ for 5 hours, and roasting at 550 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the Y-type molecular sieve is 15%.
(2) And (2) immersing the mixed solution of ammonium metatungstate and nickel nitrate into the modified alumina carrier prepared in the step (1), drying at 110 ℃ for 3 hours, and roasting at 450 ℃ for 3 hours to obtain the catalyst DC-2.
The catalyst DC-2 comprises the following components in percentage by weight: WO (WO) 3 20 percent of nickel oxide, 6.0 percent of nickel oxide and the balance of carrier.
Comparative example 3
(1) Uniformly mixing a Y-type molecular sieve with alumina powder, nitric acid, starch and deionized water, wherein the Y-type molecular sieve is as follows: alumina powder: nitric acid: starch: the mass ratio of deionized water is 15:75:4:3:60, then kneading and extruding strips for molding, then drying at 120 ℃ for 10 hours, and roasting at 700 ℃ for 3 hours to obtain the modified alumina carrier, wherein the content of the Y-type molecular sieve is 15%.
(2) And (3) dipping the ammonium metatungstate solution into the modified alumina carrier prepared in the step (1), drying at 110 ℃ for 3 hours, and roasting at 350 ℃ for 3 hours to obtain a catalyst precursor.
(3) And (3) dipping the nickel nitrate solution into the catalyst precursor prepared in the step (2), drying at 80 ℃ for 3 hours, and roasting at 250 ℃ for 3 hours to obtain the catalyst DC-3.
The catalyst DC-3 comprises the following components in percentage by weight: WO (WO) 3 20 percent of nickel oxide, 8.0 percent of nickel oxide and the balance of carrier.
For the C-1 to C-8 catalysts prepared in the above examples, the DC-1 to DC-3 catalysts (oxidized state) prepared in the comparative examples were prepared with a molar ratio of +4 valence Mo/W to the total Mo/W (i.e., mo 4+ /W 4+ Content), mole ratio of +4 valence Mo/W of hydrogenation catalyst (sulfided) to total Mo/W (i.e., mo) 4+ /W 4+ Content) is shown in table 1.
Table 1.
Taking fig. 1 as an example, the implementation process of the method for increasing yield of ethylene cracking raw materials of the invention is as follows: the oil product raw material 1 enters a flash evaporation zone 4 under certain temperature and pressure conditions, and is subjected to gas-liquid separation into a gas phase and a liquid phase in the flash evaporation zone 4. The gas phase flows upward into the gas phase reaction zone 3, and the liquid phase flows downward into the gas-liquid countercurrent reaction zone 5. The hydrogen 2 enters the reactor from the bottom of the reactor, and after being mixed and contacted with the liquid phase material flowing downwards in the gas-liquid countercurrent reaction zone 5, the excessive hydrogen continues to flow upwards to enter the gas-phase reaction zone 3, the gas-phase hydrogenation product 6 is collected at the top of the gas-phase reaction zone 3, and the heavy phase hydrogenation product 7 is collected at the bottom of the gas-liquid countercurrent reaction zone 5.
In the gas phase reaction zone 3, the light component hydrodeolefine reaction mainly occurs, and the generated gas phase hydrogenation product 6 is an ethylene cracking component. The liquid phase obtained by flash evaporation in the gas-liquid countercurrent reaction zone 5 flows downwards, hydrogen flows upwards, and the gas-liquid countercurrent contact generates hydrocracking reaction and deep hydrodesulfurization and denitrification reaction. The hydrogen sulfide and light components generated by the reaction flow upwards along with the gas-phase material flow to enter the gas-phase reaction zone 3, then the hydrogenation and olefin removal reaction also occurs, and the hydrogen sulfide and the light components flow out of the device from the top of the reactor. The heavy phase hydrogenation product 7 after liquid phase hydrogenation flows downwards out of the reactor.
Examples 9 to 16
The gas phase reaction zone and the gas-liquid countercurrent reaction zone of the embodiment are both provided with a catalyst bed layer. The gas phase reaction zone was charged with a conventional Ni-Mo hydrogenation catalyst (alumina as a carrier, 4.2% as active ingredient Ni as oxide, 16.8% as oxide, and prepared by conventional impregnation). The catalysts C-1 to C-8 prepared in examples 1 to 8 were packed in the gas-liquid countercurrent reaction zone, respectively. The temperature of the reaction bed layer in each reaction zone in the reaction process is stable and controllable. The catalyst properties are shown in Table 1, the raw oil is mixed oil of straight firewood, catalytic firewood and Jiao Chai, and the ratio of the three is 40:30:30, the properties of the raw oil are shown in Table 2, and the reaction process conditions and results are shown in tables 3 and 4.
Comparative examples 4 to 6
The gas phase reaction zone and the gas-liquid countercurrent reaction zone of the comparative example are both provided with a catalyst bed. The gas phase reaction zone was charged with the same conventional Ni-Mo hydrogenation catalyst as in the above example, and the gas-liquid countercurrent reaction zone was charged with the catalysts DC-1 to DC-3 prepared in comparative examples 1 to 3, respectively. The properties of the raw oil are the same as those of the examples, and the reaction process conditions and the results are shown in Table 4.
Comparative example 7
The method for increasing yield of ethylene cracking raw materials in the prior art is adopted, raw oil and hydrogen enter a reactor from the top of the reactor, products flow out from the bottom of the reactor, are sequentially introduced into a hydrotreating reactor (filled with a conventional Mo-Ni type hydrogenation catalyst which is the same as that in the above embodiment), a hydrocracking reaction zone (filled with a catalyst C-1), and then are fractionated to obtain ethylene cracking components. The properties of the raw oil are the same as those of the examples, and the reaction process conditions and the results are shown in Table 4.
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from tables 3 and 4, compared with comparative examples 4-7, the special reactor process flow design and the special catalyst are matched, so that the ethylene cracking raw material components can be increased under the conditions of simple flow and mild conditions.
Claims (17)
1. A method for increasing yield of ethylene cracking raw material, which is characterized in that a reactor with the following structure is adopted:
the reactor is a fixed bed reactor, an oil product raw material inlet is arranged at the middle section of the fixed bed reactor, the raw material inlet is connected with a flash evaporation zone, the upper part of the flash evaporation zone is a gas phase reaction zone, the lower part of the flash evaporation zone is a gas-liquid countercurrent reaction zone, the bottom of the fixed bed reactor is provided with a hydrogen inlet, the top of the gas phase reaction zone is provided with a gas phase hydrogenation product outlet, and the bottom of the gas-liquid countercurrent reaction zone is provided with a heavy phase hydrogenation product outlet; the hydrocracking catalyst with high cracking performance and high nitrogen poisoning resistance is filled in the gas-liquid countercurrent reaction zone, and comprises a carrier and an active component, wherein the carrier is a mixture of a molecular sieve and alumina, and the molecular sieve accounts for 5-25wt% based on the total weight of the carrier; the active components are VIB metal sulfide and VIII metal oxide, the total weight of the catalyst is 2-30% of the VIB metal sulfide, the VIII metal oxide is 2-10% of the oxide, the VIB metal sulfide is loaded on a molecular sieve, and the VIII metal oxide is loaded on the molecular sieve and alumina;
the method for increasing the yield of the ethylene cracking raw material comprises the following steps: the oil product is sent into a flash evaporation zone of a fixed bed reactor, the oil product is separated into a liquid phase component and a gas phase component after flash evaporation, the gas phase component upwards enters a gas phase reaction zone to carry out hydrogenation and olefin removal reaction, and a reaction product is discharged from a gas phase hydrogenation product outlet at the top of the reactor; the liquid phase component after flash evaporation enters a gas-liquid countercurrent reaction zone downwards, hydrodesulfurization, denitrification and cracking reactions are carried out under the action of a filled hydrocracking catalyst, the light component obtained by the cracking reaction enters a gas phase reaction zone upwards for hydrodeolefination reaction, and the heavy component obtained by the cracking reaction flows out as a product from a heavy phase hydrogenation product outlet;
the hydrocracking catalyst is prepared by the following method:
(1) Impregnating a molecular sieve with impregnating solution containing VIB group metal, and carrying out ultrasonic treatment, drying, roasting and vulcanization treatment to obtain a modified molecular sieve;
(2) Mixing the modified molecular sieve in the step (1), alumina, a peptizing agent and an extrusion aid, extruding to form strips, and drying and roasting in an inert atmosphere to obtain a modified alumina carrier;
(3) Impregnating the modified alumina carrier in the step (2) with an impregnating solution containing a group VIII metal, and then drying and roasting in an inert atmosphere to obtain the hydrocracking catalyst.
2. The process of claim 1 wherein the support is a mixture of molecular sieve and alumina, the molecular sieve comprising 8 to 20wt% based on the total weight of the support.
3. The process according to claim 1, wherein the active components are a group VIB metal sulfide and a group VIII metal oxide, the group VIB metal sulfide being 15-28% by sulfide and the group VIII metal oxide being 4-8% by oxide, based on the total weight of the catalyst.
4. The method of claim 1 further comprising subjecting the heavy phase hydrogenation product to a liquid phase hydrogenation process to further co-produce ultra low sulfur, low polycyclic aromatic hydrocarbon high quality diesel blending components.
5. The process according to claim 1, wherein the hydrocracking catalyst, when present in the oxidic state, when analyzed by XPS spectroscopy, has a molar proportion of group VIB metal in the +4-valent state of 60% -90% of the total amount of group VIB metals.
6. The process according to claim 1, characterized in that the hydrocracking catalyst, when present in sulfided form, when analyzed by XPS spectroscopy, has a molar proportion of group VIB metal in +4 valence state of 65% to 100% of the total amount of group VIB metal.
7. The method according to claim 1, wherein the group VIB metal sulfide is molybdenum sulfide or/and tungsten sulfide and the group VIII metal oxide is nickel oxide or/and cobalt oxide; the molecular sieve is at least one selected from a Y-type molecular sieve, a ZSM-5 molecular sieve, a beta-type molecular sieve and an MCM-41 molecular sieve.
8. The process of claim 1 wherein the hydrocracking catalyst is one that does not require in-situ presulfiding at the time of use.
9. The method of claim 1, wherein the drying conditions of step (1) are: drying at 90-200deg.C for 3-6 hr; the roasting condition is that the roasting temperature is 300-500 ℃ and the roasting time is 2-6 hours.
10. The method according to claim 1, wherein the drying temperature in step (2) is 20 to 90 ℃ and the drying time is 4 to 16 hours; the roasting temperature is 500-800 ℃ and the roasting time is 2-5 hours.
11. The method of claim 1, wherein the inert atmosphere of step (2) and step (3) is N 2 And one or more of inert gases.
12. The method according to claim 1, wherein the drying temperature in step (3) is 20 to 90 ℃ and the drying time is 4 to 16 hours; the roasting temperature is 200-400 ℃ and the roasting time is 2-5 hours.
13. The method of claim 1, wherein the oil feedstock is selected from one or more of straight run diesel, catalytically cracked diesel, coker diesel, ebullated bed residuum hydrogenated diesel.
14. The process of claim 1 wherein the flash zone is configured to separate light fractions below 240 ℃ from the feedstock as a vapor phase component into the vapor phase reaction zone and heavy fractions above 240 ℃ as a liquid phase component into the vapor-liquid countercurrent reaction zone.
15. The method according to claim 1, wherein the gas phase reaction zone is used for hydrogenation and olefin removal of gas phase components, and is filled with Mo-Ni and/or Mo-Co type light distillate hydrogenation catalyst.
16. The method according to claim 1The method is characterized in that the process conditions of the gas phase reaction zone are that the pressure is 1.0-10.0 MPa, wherein the hydrogen partial pressure accounts for 50-70% of the total pressure; volume space velocity is 0.1-12.0 h -1 The feeding temperature is 130-300 ℃, and the hydrogen-oil volume ratio is 10:1 to 1000:1.
17. the method according to claim 1, wherein the process conditions of the gas-liquid countercurrent reaction zone are that the pressure is 1.0-12.0 MPa, and the hydrogen partial pressure accounts for 60% -90% of the total pressure proportion; volume space velocity is 0.1-10.0 h -1 The reaction temperature is 220-450 ℃; hydrogen oil volume ratio 10:1 to 1000:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101343562A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrodesulphurization, olefin reduction method for gasoline |
| CN101343563A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrotreating process for light hydrocarbons |
| CN101376837A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Diesel deep desulfurization and dearomatization hydrotreating process |
| CN108014781A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343562A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrodesulphurization, olefin reduction method for gasoline |
| CN101343563A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrotreating process for light hydrocarbons |
| CN101376837A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Diesel deep desulfurization and dearomatization hydrotreating process |
| CN108014781A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
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