CN116515525A - Residual oil alkali metal treatment-catalytic cracking combined processing method - Google Patents
Residual oil alkali metal treatment-catalytic cracking combined processing method Download PDFInfo
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- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 105
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 81
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 72
- 238000003672 processing method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000926 separation method Methods 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003502 gasoline Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000007790 solid phase Substances 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000000571 coke Substances 0.000 claims abstract description 11
- 239000002283 diesel fuel Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- -1 alkali metal nitride Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 108
- 238000005984 hydrogenation reaction Methods 0.000 description 20
- 238000005516 engineering process Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
-
- 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
- C10G2300/1077—Vacuum residues
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a residual oil alkali metal treatment-catalytic cracking combined processing method, which comprises the following steps: (1) Mixing residual oil raw materials and alkali metals, and reacting in a reactor; (2) The materials after the reaction in the step (1) are subjected to solid-liquid separation to obtain solid-phase products and generated oil; (3) And (3) feeding the generated oil obtained in the step (2) into a catalytic cracking device, and fractionating the reacted material to obtain dry gas, liquefied gas, catalytic cracking gasoline, catalytic cracking light diesel oil, catalytic cracking heavy distillate oil and coke. The method can produce high-quality low-sulfur gasoline fractions, has long operation period, does not need high-temperature high-pressure conditions and has low hydrogen consumption, thereby effectively improving the fuel quality, reducing the operation cost of the device and realizing energy conservation and consumption reduction.
Description
Technical Field
The invention belongs to the field of residual oil processing and utilization, and in particular relates to a residual oil alkali metal treatment-catalytic cracking combined processing method.
Background
With the increasing shortage of world petroleum resources and the trend of heavy and poor quality of crude oil, the deep processing technology of residuum represented by the combined process of residuum hydrotreatment and catalytic cracking is widely focused.
Regarding the traditional residuum hydrogenation technology, the technology comprises four process types of a fixed bed, an ebullated bed, a moving bed and a suspension bed, has the advantages of high oil yield, adjustable and controllable olefin and aromatic hydrocarbon content, and the like, but has high reaction severity, high hydrogen consumption and low hydrodesulfurization selectivity, so that the non-traditional hydrotreating technology in recent years becomes a research hot spot in the petrochemical industry field. The residual oil alkali metal treatment technology does not need high-temperature high-pressure reaction conditions, does not need a catalyst, has long operation period and high desulfurization selectivity, shows excellent denitrification and demetallization performances, and can completely replace the traditional hydrogenation technology.
The main problems existing at present for a catalytic cracking device are high coke yield, low product yield and poor quality of catalytically cracked light diesel.
CN106701189a discloses a combined process of residuum hydrotreatment-catalytic cracking. The invention organically combines fixed bed residual oil hydrogenation with catalytic cracking technology, but the fixed bed residual oil hydrogenation technology has the problems of easy catalyst deactivation, short operation period and the like, and even if the raw material property Ni+V is controlled to be less than 105ppm, the carbon residue is controlled to be less than 15 percent, the operation period is only 1 year, and the catalyst cannot be matched with the long-period operation (3-5 years) of a catalytic cracking device.
CN103102985a discloses a combined process for hydrotreating and catalytic cracking of residuum. The invention relates to a boiling bed residual oil hydrogenation technology, which has the problems of high reaction severity, high hydrogen consumption and the like as a traditional hydrogenation technology although a catalyst can be replaced on line and the operation period is long. In addition, the traditional residual oil hydrogenation technology has poor desulfurization selectivity, can cause a great deal of saturation of olefin and aromatic hydrocarbon in the deep hydrodesulfurization process, and reduces the quality of fuel oil.
US4713221 discloses a combined process of residuum hydrogenation and catalytic cracking, in which catalytically cracked heavy cycle oil is recycled to a residuum hydrogenation apparatus, mixed with residuum, hydrogenated, and then fed into the catalytic cracking apparatus. The catalytic cracking slurry oil is not effectively utilized in the invention, so the method has limited effects of reducing the coke yield and improving the product yield.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a residual oil alkali metal treatment-catalytic cracking combined processing method. The method can produce high-quality low-sulfur gasoline fractions, has long operation period, does not need high-temperature high-pressure conditions and has low hydrogen consumption, thereby effectively improving the fuel quality, reducing the operation cost of the device and realizing energy conservation and consumption reduction.
A residuum alkali metal treatment-catalytic cracking combined processing method, comprising the steps of:
(1) Mixing residual oil raw materials and alkali metals, and reacting in a reactor;
(2) The materials after the reaction in the step (1) are subjected to solid-liquid separation to obtain solid-phase products and generated oil;
(3) And (3) feeding the generated oil obtained in the step (2) into a catalytic cracking device, and fractionating the reacted material to obtain dry gas, liquefied gas, catalytic cracking gasoline, catalytic cracking light diesel oil, catalytic cracking heavy distillate oil and coke.
In step (1) of the process of the present invention, the residuum feedstock comprises atmospheric residuum, vacuum residuum, or heavy oils of other origin.
In the step (1) of the method, the alkali metal comprises one or more of lithium (Li), sodium (Na) and potassium (K).
In the step (1) of the method, the reactor is a kettle type reactor with stirring, and the stirring speed is 300-1500r/min, preferably 500-1000r/min.
In step (1) of the process of the present invention, the residual oil feedstock and the alkali metal are mixed and reacted in the presence of hydrogen, and the reaction involves desulfurization, denitrification, demetallization, thermal cracking, etc.
In the step (1) of the method, the reaction operation conditions are as follows: the reaction temperature is 250-400 ℃, the hydrogen partial pressure is 1.0-18.0MPa, the molar ratio of alkali metal to sulfur content of raw material is 1-5, and the hydrogen oil volume ratio is 100-1000Nm 3 /m 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferred operating conditions are: the reaction temperature is 300-370 ℃, the hydrogen partial pressure is 3.0-16.0MPa, and the alkali gold isThe molar ratio of sulfur content to raw material is 2-4, and the volume ratio of hydrogen oil is 300-800Nm 3 /m 3 。
In the step (2) of the method, the separation device comprises various equipment capable of realizing solid-liquid separation, such as a horizontal screw type centrifuge, a disc type separator, a cyclone and a filtering separator; the separation device is preferably a horizontal decanter centrifuge, and the rotation speed is 2500-10000r/min, preferably 3500-9000r/min.
In the step (2) of the method, the solid phase product contains substances such as alkali metal sulfide, alkali metal nitride, heavy metal and the like.
In step (2) of the method of the present invention, the solid content in the produced oil is controlled to be 50 to 500ppm, preferably 1 to 200ppm, and the acid value of the produced oil is controlled to be less than 1.0mgKOH/g, preferably less than 0.5mgKOH/g.
In the step (2) of the method, the solid-liquid separation is carried out for at least 2 times, and a solid phase product 1 and a generated oil 1 are obtained through one-time solid-liquid separation; adding an acidic additive into the generated oil 1 for secondary solid-liquid separation to obtain a solid-phase product 2 and the generated oil 2. Controlling the solid content in the generated oil 1 to be 1500-3000ppm, preferably 1200-2500ppm; the base number is 15-30mgKOH/g, preferably 11-20mgKOH/g. The acidic additive comprises one or more of formic acid, hydrochloric acid, trichloroacetic acid and phosphoric acid, and is preferably added with stirring, and is further preferably added with stirring at a suitable temperature, generally 100-330 ℃, preferably 150-300 ℃. The stirring rate is generally 50 to 1500r/min, preferably 150 to 1200r/min. The solid content in the produced oil 2 obtained after the secondary solid-liquid separation is controlled to be 50-600ppm, preferably 1-200ppm, and the acid value of the produced oil 2 after the addition of the acidic substance is less than 1.0mgKOH/g, preferably less than 0.5mgKOH/g.
The solid phase product obtained in the step (2) of the method is further separated, and heavy metals are separated and led out of the device; the alkali metal sulfide and the alkali metal nitride are regenerated in the regeneration device to generate alkali metal, elemental sulfur and nitrogen, wherein the alkali metal is returned to the reaction zone, and the elemental sulfur and the nitrogen are led out of the device. The regeneration device is a device/process which can realize alkali metal regeneration, such as alkali metal electrolysis regeneration process technology developed by Ceramatec Inc, salt LakeCity, utah company.
In the step (3) of the method, the generated oil 2 obtained in the step (2) is singly or mixed with other raw materials and then enters a catalytic cracking device, and the reacted materials are fractionated to obtain dry gas, liquefied gas, catalytic cracking gasoline, catalytic cracking light diesel oil, catalytic cracking heavy distillate oil and coke.
In the step (3) of the method, the catalytic cracking heavy distillate oil can be mixed with the residual oil raw material in the step (1) and then mixed with alkali metal for reaction. The mixing of the catalytic cracking heavy fraction and the residual oil raw material can reduce the impurity content and improve the catalytic cracking performance of the catalytic cracking heavy fraction oil serving as catalytic cracking feed, thereby improving the yields of high-quality low-sulfur gasoline fraction and diesel oil fraction.
In step (3) of the process of the present invention, the catalytic cracking unit may employ conventional techniques in the art. The catalytic cracking device can be one set or more than one set, and each set of device at least comprises one reactor and one regenerator. The catalytic cracking device is provided with a fractionating tower, and each set of catalytic cracking device can be respectively set or shared. The reactor may be a catalytic cracking reactor of various types, preferably a riser reactor.
In step (3) of the process of the present invention, the catalytic cracking unit may be operated under conditions typical in the art: the reaction temperature is 400-700 ℃, the reaction pressure is 0.1-0.8MPa, the catalyst-oil ratio (weight) is 2-60, and the contact time of the reaction raw materials and the catalyst is 0.1-30s. Preferred operating conditions are: the reaction temperature is 460-550 ℃, the reaction pressure is 0.1-0.4MPa, the catalyst-oil ratio (weight) is 5-20, and the contact time of the reaction raw materials and the catalyst is 0.1-10s.
In step (3) of the method, the catalytic cracking catalyst filled in the catalytic cracking device comprises various types of catalytic cracking catalysts, such as acid-treated clay, silica-alumina catalyst and ZSM-5 type, X type, Y type and other molecular sieve catalysts.
In the residual oil alkali metal treatment unit, residual oil raw material and/or catalytic cracking heavy distillate oil are subjected to desulfurization, denitrification, demetallization, thermal cracking and other reactions under the action of alkali metal and hydrogen. Because of high alkali metal reactivity, the sulfur, nitrogen and metal content in the residual oil raw material can be greatly reduced under mild conditions. As a raw material of the catalytic cracking unit, the high-quality low-sulfur gasoline fraction can be directly produced, the contents of sulfur oxides and nitrogen oxides in catalytic cracking flue gas can be greatly reduced, and in addition, the deactivation of a catalytic cracking catalyst can be effectively slowed down due to the reduction of the contents of metal and nitrogen. The catalytic cracking heavy distillate oil is circulated to the hydrogenation upgrading reaction zone of the alkali metal method, so that the viscosity of the residual oil raw material can be reduced, the dispersity of the alkali metal in the reaction system can be improved, and the reaction rate and impurity removal effect can be improved. Meanwhile, the heavy fraction oil of catalytic cracking can remove impurities in an alkali metal hydrogenation upgrading unit to become better catalytic cracking feed, so that the yield of the catalytic cracking high value-added product is further improved.
The acidic additive is utilized in the separation unit to effectively remove alkaline substances such as residual alkali metal, alkali metal sulfide and the like in the residual oil generated by the residual alkali metal treatment device, so that the alkaline substances are prevented from entering the catalytic cracking device to inactivate the catalytic cracking acidic catalyst.
Compared with the prior art, the residual oil processing method has the following advantages:
(1) The residual oil alkali metal treatment-catalytic cracking combined process provided by the invention uses residual oil and catalytic cracking heavy distillate oil as raw materials, and can produce high-quality low-sulfur gasoline fraction with high yield.
(2) Compared with the traditional hydrotreating technology, the residual oil alkali metal treatment technology has low reaction severity, and does not need high-temperature high-pressure reaction conditions; the catalyst is not needed, the waste agent treatment problem is avoided, the device investment can be effectively reduced, and the energy conservation, consumption reduction and environmental protection are facilitated.
(3) And (3) treating the oil generated by the residual oil alkali metal treatment device to remove alkaline substances such as residual alkali metal, alkali metal sulfide and the like in the generated oil, so as to avoid the alkaline substances from entering the catalytic cracking device to inactivate the catalytic cracking acidic catalyst.
(4) The high-quality low-sulfur gasoline fraction can be directly produced by carrying out hydrogenation upgrading treatment on the catalytic cracking raw material, so that the follow-up gasoline hydrofining and the treatment measures of exceeding the standard of sulfur oxide, nitrogen oxide and other contents of catalytic cracking flue gas are omitted, and the types and the number of devices are reduced.
(5) The invention circulates the catalytic cracking heavy distillate oil to the residual oil alkali metal treatment upgrading unit for further hydrogenation upgrading, thereby achieving two purposes: firstly, the addition of the catalytic cracking heavy distillate reduces the viscosity of the residual oil raw material, is beneficial to improving the dispersity of alkali metal in a reaction system, and further improves the reaction rate and impurity removal effect; secondly, the heavy fraction oil after catalytic cracking is further removed of impurities in a residual oil alkali metal treatment unit, so that the heavy fraction oil becomes better catalytic cracking feed, and the yield of high value-added products can be improved.
(6) The catalytic cracking products are separated into catalytic gasoline, catalytic cracking light diesel oil and catalytic cracking heavy distillate oil, and the catalytic cracking circulating oil and the catalytic cracking slurry oil are not separately fractionated, so that the structure of a fractionating tower can be simplified, and the investment of the device and the energy consumption of operation are reduced.
Drawings
FIG. 1 is a flow chart of a combined processing method of alkali metal treatment-catalytic cracking of residuum.
Wherein 1 is a residual oil alkali metal treatment device, 2 is a separation device, 3 is a regeneration device, 4 is a purification treatment device, 5 is a separation device, 6 is a catalytic cracking device, 7 is a separation device, 8 is alkali metal, 9 is hydrogen, 10 is a residual oil raw material, 11 is a residual oil alkali metal treatment product, 12 is a residual oil alkali metal treatment solid phase product (alkali metal sulfide and alkali metal nitride), 13 is alkali metal, 14 is a residual oil alkali metal treatment generated oil, 15 is an acidic additive, 16 is a purification treated product (generated oil and alkali metal salt), 17 is a purification treated generated oil, 18 is nitrogen, 19 is elemental sulfur, 20 is heavy metal, 21 is hydrogen and hydrogen sulfide, 22 is a dry gas, 23 is liquefied gas, 24 is gasoline, 25 is diesel, 26 is heavy cycle oil, 27 is coke, 28 is alkali metal salt, 29 is a catalytic cracking heavy cycle oil from which catalyst powder is removed, and 30 is catalyst powder.
Detailed Description
The method provided by the invention is described below with reference to the accompanying drawings. The residuum feedstock from line 10 is mixed with catalytically cracked heavy distillate from line 29, then mixed with hydrogen from line 9 and with alkali metal from line 8 and regenerated alkali metal from line 13 before entering residuum alkali metal treatment unit 1 for reaction. The reaction product enters the separator 2 through a pipeline 11 for solid/liquid separation, wherein the solid phase product enters the regenerator 3 through a pipeline 12, and non-renewable heavy metals are extracted through a pipeline 20; the solid alkali metal sulfide and the alkali metal nitride are regenerated to generate metal sodium, elemental sulfur and nitrogen, and the regenerated metal sodium is returned to the residual alkali metal treatment reactor through a pipeline 13, and the elemental sulfur and the nitrogen are respectively extracted through pipelines 19 and 18. The produced oil (produced oil 1) obtained after the solid-liquid separation is introduced into the purification treatment apparatus 4 through a line 14, and reacted with an acidic additive from a line 15 to obtain hydrogen gas, hydrogen sulfide, and a solid-liquid mixture. Hydrogen and hydrogen sulfide are withdrawn through line 21, the solid-liquid mixture is fed through line 16 to separation unit 5 for separation to obtain purified product oil and alkali metal salt, and the alkali metal salt is withdrawn through line 28. The purified produced oil (produced oil 2) enters a catalytic cracking device 6 through a pipeline 17 to carry out cracking reaction, and is separated into dry gas, liquefied gas, catalytic gasoline, catalytic cracking light diesel oil, catalytic cracking heavy fraction and coke through a fractionation facility, wherein the dry gas, the liquefied gas, the catalytic gasoline, the catalytic cracking light diesel oil and the coke are respectively extracted through pipelines 22, 23, 24, 25 and 27, and the catalytic cracking heavy fraction oil enters a separation device through a pipeline 26 to remove catalyst powder and then returns to a residual oil alkali metal treatment unit through a pipeline 29. The removed catalyst fines are withdrawn via line 30.
The following examples are provided to further illustrate the process of the present invention, but are not intended to limit the invention.
The experiments in the examples and comparative examples were performed on laboratory autonomous residuum alkali metal treatment pilot plants and small riser catalytic cracking units. The separation device is a horizontal screw type centrifuge, and the generated oil purification device is a reaction tank with mixing equipment. The alkali metal used is sodium metal. The acid additive is a mixture of formic acid and phosphoric acid, and the mixing mass ratio is 1:1. the catalytic cracking catalyst used was an LC-7 type catalyst produced by Lanzhou petrochemical catalyst plant.
The calculation formula of the single pass conversion rate of the catalytic cracking in the examples and the comparative examples is as follows: single pass conversion= [ gas+gasoline+coke)/total feed ] 100% and the activity of the catalyst is compared based on conversion.
The residuum feed a used in the examples and comparative examples was taken from a refinery atmospheric and vacuum unit and the properties are shown in table 1.
Example 1
In this example, the residuum is hydroconverted using a combined residuum alkali metal treatment and catalytic cracking process. Residual oil raw material A, catalytic cracking heavy distillate oil and hydrogen are mixed and then mixed with metal sodium, and then enter an alkali metal hydrogenation upgrading reaction zone for reaction. The reaction product enters a horizontal screw type centrifuge for solid-liquid separation to obtain modified generated oil and solid phase, and the rotational speed of the centrifuge is 4200r/min. Purifying the obtained modified generated oil, and reacting with an acidic additive in a purifying device to remove alkaline impurities under the conditions of 250 ℃ and stirring speed of 800r/min. Then the solid impurities are removed by a horizontal screw type centrifuge (the rotating speed is 8000 r/min) and enter a catalytic cracking device. The acid additive is excessively added, and the excessive acid additive is removed by a water washing device.
Comparative example 1
The comparative example uses a fixed bed residuum hydrogenation and catalytic cracking combined process to conduct residuum hydroconversion. Residual oil raw material A, catalytic cracking heavy distillate oil and hydrogen are mixed and then enter fixed bed residual oil hydrogenation for reaction. The obtained generated oil enters a catalytic cracking device. The fixed bed catalyst adopts industrial devices to use commercial catalysts FZC-28, FZC-30 and FZC-41 which are developed and produced by the smooth petrochemical industry institute, and the fixed bed reactor is filled with the catalysts FZC-28, FZC-30 and FZC-41, and the filling volume ratio is 3:2:1.
the reaction conditions of the residual oil alkali metal treatment, the fixed bed residual oil hydrogenation and the catalytic cracking are shown in Table 2, the properties of the residual oil alkali metal treatment and the fixed bed residual oil hydrogenation oil production are shown in Table 3, and the product distribution and properties of the catalytic cracking device are shown in tables 4 and 5. It can be seen that under the mild reaction condition of 340 ℃ and 10MPa, the desulfurization rate, demetallization rate and carbon residue removal rate of the residual oil alkali metal treatment technology are obviously superior to those of the oil produced by the fixed bed residual oil hydrogenation device, and further, after the oil treated by the residual oil alkali metal treatment technology is subjected to cracking reaction in the catalytic cracking device, the gasoline yield is higher, and the sulfur content of the gasoline fraction is lower (26.4 ppm). Therefore, the residual oil alkali metal treatment-catalytic cracking combined process technology can fully exert the advantages of the residual oil alkali metal treatment technology, and the technology has low reaction severity and does not need high-temperature and high-pressure reaction conditions; the catalyst is not needed, the waste agent treatment problem is avoided, the device investment can be effectively reduced, and the energy conservation, consumption reduction and environmental protection are facilitated.
TABLE 1 Properties of the feedstock
TABLE 2 main operating conditions for residuum alkali metal treatment and catalytic cracking
TABLE 3 alkali metal treatment of residuum and hydrogenation of fixed bed residuum to oil quality
TABLE 4 catalytic cracker product distribution
TABLE 5 catalytic cracking gasoline principal Properties
Example 2
In this example, residue feed a was used and the process was the same as in example 1. The rotating speed of the one-time separation horizontal decanter centrifuge is 4800r/min. In the secondary separation process, the temperature of the purification treatment device is 300 ℃, the stirring speed is 1100r/min, and the rotating speed of the horizontal decanter centrifuge is 8000r/min.
Example 2-1
Compared with the example 2, the residual oil alkali metal treatment generated oil is separated once, and the rotating speed of the horizontal decanter centrifuge is 9000r/min.
The reaction conditions of the residual oil alkali metal treatment, the purification unit and the catalytic cracking are shown in Table 6, the oil formation properties of the residual oil alkali metal treatment device are shown in Table 7 and Table 8, and the catalyst activity after 200 hours is shown in Table 9. As can be seen from Table 9, the catalytic cracking catalyst activity after 200 hours of operation in example 2 was 7.1 percent higher than that in example 2-1, indicating that the secondary separation process can effectively remove alkaline substances in the oil produced by the residual alkali metal treatment device, and avoid the decrease of the concentration of the acid center of the catalyst caused by the alkaline substances, thereby reducing the catalyst activity.
Example 3
In this example, residue feed a was used and the process was the same as in example 1. The rotating speed of the primary separation horizontal decanter centrifuge is 3500r/min. In the secondary separation process, the temperature of the purification treatment device is 180 ℃, the stirring speed is 300r/min, and the rotating speed of the horizontal decanter centrifuge is 8000r/min.
Example 3-1
Compared to example 3, the rotational speed of the one-time separation decanter centrifuge is 6300r/min. The parameters of the secondary separation process were the same as in example 3.
As can be seen from Table 8, the increase in the rotational speed of the decanter centrifuge during the first separation in example 3-1 reduced the solids content of the produced oil 1, but the solids content of the produced oil 2 was slightly higher than that of example 2. The reason is that the removal rate of solid phase substances is higher in the primary separation process, and the residual solid phase suspended substances are more, so that the deposition of the solid phase substances in the secondary separation process is not facilitated.
TABLE 6 main operating conditions for residuum alkali metal treatment and catalytic cracking
TABLE 7 oil Properties produced by residuum alkali Metal treatment plant
TABLE 8 oil Properties produced by residuum alkali Metal treatment plant
TABLE 9 catalytic cracking catalyst Activity after 200h reaction
| Project | Example 2 | Example 2-1 | Example 3 | Example 3-1 |
| Single pass conversion, wt.% | 64.3 | 57.2 | 61.2 | 59.8 |
Claims (18)
1. A residual oil alkali metal treatment-catalytic cracking combined processing method is characterized in that: the method comprises the following steps:
(1) Mixing residual oil raw materials and alkali metals, and reacting in a reactor;
(2) The materials after the reaction in the step (1) are subjected to solid-liquid separation to obtain solid-phase products and generated oil;
(3) And (3) feeding the generated oil obtained in the step (2) into a catalytic cracking device, and fractionating the reacted material to obtain dry gas, liquefied gas, catalytic cracking gasoline, catalytic cracking light diesel oil, catalytic cracking heavy distillate oil and coke.
2. The method according to claim 1, characterized in that: in the step (1), the residual oil raw materials comprise atmospheric residual oil and vacuum residual oil.
3. The method according to claim 1, characterized in that: in the step (1), the alkali metal comprises one or more of lithium (Li), sodium (Na) and potassium (K).
4. The method according to claim 1, characterized in that: in the step (1), the reactor is a stirred tank reactor, and the stirring speed is 300-1500r/min, preferably 500-1000r/min.
5. The process according to claim 1, wherein in step (1), the residual oil feedstock and the alkali metal are mixed and reacted in the presence of hydrogen.
6. The method according to claim 5, wherein: in the step (1), the reaction operation conditions are as follows: the reaction temperature is 250-400 ℃, the hydrogen partial pressure is 1.0-18.0MPa, the molar ratio of alkali metal to sulfur content of raw material is 1-5, and the hydrogen oil volume ratio is 100-1000Nm 3 /m 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferred operating conditions are: the reaction temperature is 300-370 ℃, the hydrogen partial pressure is 3.0-16.0MPa, the molar ratio of alkali metal to sulfur content of raw material is 2-4, and the hydrogen oil volume ratio is 300-800Nm 3 /m 3 。
7. The method according to claim 1, characterized in that: in the step (2), the separation device is one of a horizontal decanter centrifuge, a disc separator, a cyclone and a filtering separator; the preferred separation device is a decanter centrifuge with a rotational speed of 2500-10000r/min, preferably 3500-9000r/min.
8. The method according to claim 1, characterized in that: in the step (2), the solid content in the produced oil is controlled to be 50-500ppm, preferably 1-200ppm, and the acid value of the produced oil is controlled to be less than 1.0mgKOH/g, preferably less than 0.5mgKOH/g.
9. The method according to claim 1, characterized in that: in the step (2), the solid-liquid separation is carried out for at least 2 times, and a solid-phase product 1 and a generated oil 1 are obtained through one-time solid-liquid separation; adding an acidic additive into the generated oil 1 for secondary solid-liquid separation to obtain a solid-phase product 2 and the generated oil 2.
10. The method according to claim 9, wherein: controlling the solid content in the generated oil 1 to be 1500-3000ppm, preferably 1200-2500ppm; the base number is 15-30mgKOH/g, preferably 11-20mgKOH/g.
11. The method according to claim 9, wherein: the acidic additive comprises one or more of formic acid, hydrochloric acid, trichloroacetic acid and phosphoric acid, and is preferably added with stirring, and is further preferably added with stirring at a suitable temperature of 100-330 ℃, preferably 150-300 ℃.
12. The method according to claim 11, wherein: the stirring rate is 50-1500r/min, preferably 150-1200r/min.
13. The method according to claim 9, wherein: the solid content in the produced oil 2 obtained after the secondary solid-liquid separation is controlled to be 50-600ppm, preferably 1-200ppm, and the acid value of the produced oil 2 after the addition of the acidic substance is less than 1.0mgKOH/g, preferably less than 0.5mgKOH/g.
14. The method according to claim 1, characterized in that: the solid phase product obtained in the step (2) is further separated, and heavy metals are separated and led out of the device; the alkali metal sulfide and the alkali metal nitride are regenerated in the regeneration device to generate alkali metal, elemental sulfur and nitrogen, wherein the alkali metal is returned to the reaction zone, and the elemental sulfur and the nitrogen are led out of the device.
15. The method according to claim 1, characterized in that: the generated oil 2 obtained in the step (2) in the step (3) is singly or mixed with other raw materials and then enters a catalytic cracking device, and the reacted materials are fractionated to obtain dry gas, liquefied gas, catalytic cracking gasoline, catalytic cracking light diesel oil, catalytic cracking heavy distillate oil and coke.
16. The method according to claim 1, characterized in that: and (3) mixing the catalytic cracking heavy distillate oil in the step (3) with the residual oil raw material in the step (1) and then mixing with alkali metal for reaction.
17. The method according to claim 1, characterized in that: the catalytic cracker conditions described in step (3) operate as follows: the reaction temperature is 400-700 ℃, the reaction pressure is 0.1-0.8MPa, the catalyst-oil ratio (weight) is 2-60, and the contact time of the reaction raw materials and the catalyst is 0.1-30s; preferred operating conditions are: the reaction temperature is 460-550 ℃, the reaction pressure is 0.1-0.4MPa, the catalyst-oil ratio (weight) is 5-20, and the contact time of the reaction raw materials and the catalyst is 0.1-10s.
18. The method according to claim 17, wherein: the catalytic cracking catalyst filled in the catalytic cracking device in the step (3) is one or more of clay, silicon-aluminum catalyst, ZSM-5 type, X type and Y type.
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