WO2024033932A1 - Anti-cracking additive composition for reducing the cracking in a reduced crude oil vacuum heater - Google Patents
Anti-cracking additive composition for reducing the cracking in a reduced crude oil vacuum heater Download PDFInfo
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- WO2024033932A1 WO2024033932A1 PCT/IN2022/051094 IN2022051094W WO2024033932A1 WO 2024033932 A1 WO2024033932 A1 WO 2024033932A1 IN 2022051094 W IN2022051094 W IN 2022051094W WO 2024033932 A1 WO2024033932 A1 WO 2024033932A1
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- Prior art keywords
- cracking
- additive composition
- tert
- carboxylates
- butyl
- Prior art date
Links
- 238000005336 cracking Methods 0.000 title claims abstract description 72
- 239000000654 additive Substances 0.000 title claims abstract description 55
- 230000000996 additive effect Effects 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000010779 crude oil Substances 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 239000002516 radical scavenger Substances 0.000 claims abstract description 16
- 239000003849 aromatic solvent Substances 0.000 claims abstract description 15
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical group [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 claims abstract description 15
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims abstract description 13
- 239000008096 xylene Substances 0.000 claims abstract description 13
- 150000007942 carboxylates Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- -1 -tert-butyl cresols Chemical class 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims description 10
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002283 diesel fuel Substances 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical class CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 claims description 5
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 5
- 229960004337 hydroquinone Drugs 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 235000010388 propyl gallate Nutrition 0.000 claims description 5
- 239000000473 propyl gallate Substances 0.000 claims description 5
- 229940075579 propyl gallate Drugs 0.000 claims description 5
- 229940079877 pyrogallol Drugs 0.000 claims description 5
- 230000000116 mitigating effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000004939 coking Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YCPYRHIWLKVSHE-UHFFFAOYSA-N 2-[1-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound CCC(N=Cc1ccccc1O)N=Cc1ccccc1O YCPYRHIWLKVSHE-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ITLFOAWVKDKEKE-UHFFFAOYSA-N N-butylbutan-1-amine 4-methyl-2H-benzotriazole Chemical compound CC1=CC=CC=2NN=NC21.C(CCC)NCCCC ITLFOAWVKDKEKE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 150000004867 thiadiazoles 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
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/06—Vacuum distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/10—Inhibiting corrosion during distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
-
- 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
-
- 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
- C10G2300/80—Additives
Definitions
- the present invention relates to the technical field of crude oil distillation. Specifically, the present invention relates to the technical field of vacuum distillation of crude oils. More specifically, the present invention relates to the anti-cracking additive composition and use thereof in reducing the cracking in a reduced crude oil vacuum heater.
- RCO Reduced crude oil
- HWOG high hot well off gases
- furnace coil output temperature is sometimes lowered by a couple of degrees or a turbulizing steam is adjusted which affects plant performance.
- prior solutions also include addition of additive compositions to enhance distillate yield.
- CN102071047A discloses a residual oil modifier for a coking delaying device and use thereof.
- the residual oil modifier has high practicality for raw material residual oil and can effectively improve the properties of residual oil, delay coking, effectively reduce coking amount and consequently improve the yield of middle-grade distillate.
- the said modifier is prepared from 1 to 25 percent of antioxygen, 1 to 20 percent of oxidation and corrosion inhibitor, 1 to 25 percent of metal deactivator, 1 to 20 percent of dispersant and the balance of solvent, and by heating, uniformly stirring and cooling.
- CN102888241A discloses an aid for improving the yield of liquid oil in an oil delayed coking device and a preparation method for the aid.
- the aid is prepared from N,N-bis(salicylidene) propylenediamine, p-tert-butylcatechol, tetrapentaerythritol ester, octylphenol polyoxyethylene (30) ether, N,N-di-n-butyl ammonia methylbenzotriazole and a solvent.
- the aid is directly added into raw material residual oil, so that a phenomenon that a coking device is coked when heating a furnace pipe and the on-stream period is prolonged can be avoided, the generation amount of coke and dry gas is reduced, and the liquid oil yield is improved.
- CN101899327A discloses an anti-coking agent for high-temperature equipment and preparation and application thereof.
- the anti-coking agent is synthesized, by the conventional method, from the following components by weight ratio: 55%-95% of polyalkenyl succinimide esters, 3%-25% of antioxidants and 2%-20% of metal deactivators, wherein an organic solvent accounts for 50% of the total materials by weight;
- the antioxidant is particularly one or more of 2,6-di-tert-phenol, alkyldiphenylamine, N,N'-di-sec-butyl-p-phenylenediamine, p,p'-di-iso-octyldiphenylamine, N- phenyl-alpha naphthylamine and pentaerythrite tetra[beta(3,5-di-tert-butyl-4- hydroxyphenyl)propionate] ;
- the metal deactivator is particularly one or more of N,N'-
- the present invention provides an anti-cracking additive composition, wherein, the additive composition includes a H2S scavenger, an antioxidant, and a solvent.
- the H2S scavenger is selected from carboxylates of Fe, carboxylates of Ni, carboxylates of Co, carboxylates of Zn or a combination thereof.
- the antioxidant is selected from di-tert-butyl phenols, di-tert-butyl cresols, hydroquinone, pyrogallol, propylgallate, butylated hydroxylanisole or a combination thereof.
- the solvent is selected from an aromatic solvent.
- the H2S scavenger is carboxylates of Zn such as but not limited to Zinc Oleate.
- the antioxidant is di-tert-butyl cresols such as but not limited to 2,6-Di-tert-butyl-p-cresol.
- the solvent is an aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof.
- the Zinc Oleate is 2-4 % by weight
- 2,6-Di-tert-butyl-p-cresol is 50-70% by weight
- the aromatic solvent is 30-50% by weight. The weight percent is based on the total weight of the additive composition
- the present invention also provides a method for preparation of the said anti-cracking additive composition, wherein, the method includes mixing the Zinc Oleate and 2,6-Di-tert-butyl-p-cresol in a solvent.
- the solvent is an aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof.
- SKO superior kerosene oil
- LDO light diesel oil
- naphtha naphtha or a combination thereof.
- 2-4 % by weight of the Zinc Oleate, and 50-70% by weight of 2,6-Di-tert-butyl-p-cresol are mixed in 30-50% by weight of the said aromatic solvent.
- the present invention also provides a process for mitigating cracking of the reduced crude oil in a vacuum heater, wherein, the process comprises adding the said anti-cracking additive composition along with reduced crude oil into the vacuum heater.
- the said anti-cracking additive composition is added in a dosage range of 5 to 500 ppm.
- RCO Reduced Crude Oil
- HWOG hot well off gases
- RCO Reduced Crude Oil
- the cracking of RCO is a three-stage process including primary cracking, secondary cracking, and condensation of products of cracking.
- Primary Cracking is unavoidable as this is due to the cleavage of weakest bonds (carbon and hetero atoms) in the least volatile fraction. This will trim the heavier molecules of their non-core heterogeneous parts resulting in decrease of the heaviest fraction.
- the asphaltenes content does not reduce or even increases fraction wise. This also contributes to higher boiling (SIMDIS) profile of the SR.
- SIMDIS higher boiling
- the secondary cracking is dominant of the two cracking processes, as the secondary cracking is not only driven by higher heats of enthalpy, but also acidic sulphur moieties generated in situ during the primary process. This would aggravate the cracking of core part of the heavier molecules, and thus leads to the formation of gases or highly volatile distillates. Accordingly, it is necessary to control this step, by the formation of the middle distillates and limiting the formation of gases/ highly volatile distillates.
- the present disclosure provides a novel anti-cracking additive composition which when dosed along with RCO, will reduce cracking, and improve vacuum. Thus, this increases distillate yields and quality, mitigate corrosion, and also contribute to reducing amine consumption in amine absorber for HWOG.
- the additive composition as disclosed herein is specifically developed to target and to control the secondary cracking step.
- the said additive composition leads to the formation of the middle distillates and limits the formation of gases or highly volatile distillates.
- the present invention provides an anti-cracking additive composition, wherein, the additive composition includes an H2S scavenger, an antioxidant, and a solvent.
- the H2S scavenger is selected from carboxylates of Fe, carboxylates of Ni, carboxylates of Co, carboxylates of Zn or a combination thereof.
- the antioxidant is selected from di-tert-butyl phenols, di-tert-butyl cresols, hydroquinone, pyrogallol, propylgallate, butylated hydroxylanisole or a combination thereof.
- the solvent is selected from an aromatic solvent.
- the H2S scavenger is carboxylates of Zn such as but not limited to Zinc Oleate.
- the antioxidant is di-tert-butyl cresols such as but not limited to 2,6-Di-tert-butyl-p-cresol.
- the solvent is the aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof. Further, in an exemplary embodiment, the solvent is xylene.
- the present invention provides a method for preparation of the said anti-cracking additive composition, wherein, the method includes mixing an H2S scavenger, an antioxidant, and a solvent.
- the H2S scavenger is selected from carboxylates of Fe, carboxylates of Ni, carboxylates of Co, carboxylates of Zn or a combination thereof.
- the antioxidant is selected from di-tert-butyl phenols, di-tert-butyl cresols, hydroquinone, pyrogallol, propylgallate, butylated hydroxylanisole or a combination thereof.
- the solvent is selected from an aromatic solvent.
- the H2S scavenger is carboxylates of Zn such as but not limited to Zinc Oleate.
- the antioxidant is di-tert-butyl cresols such as but not limited to 2,6-Di-tert-butyl-p-cresol.
- the solvent is aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof. Further, in an exemplary embodiment, the solvent is xylene.
- 2-4 % by weight of the Zinc Oleate, and 50-70% by weight of 2,6-Di-tert-butyl-p- cresol are mixed in 30-50% by weight of the said solvent and wherein the solvent is xylene.
- the present invention provides an anti-cracking additive composition containing (i) 2-4 % by weight Zinc Oleate (ii) 50-70% by weight 2,6-Di-tert-butyl-p-cresol (iii) 30-50% by weight Xylene. The weight percent is based on the total weight of the additive composition.
- the said anti-cracking additive composition acts as an anti-cracking additive to mitigate cracking in a reduced crude oil vacuum heater and improve vacuum during vacuum distillation operations.
- the cracking experiments were conducted in a Mini Pot Still equipment using Reduced Crude oils of high sulphur crudes.
- the cracking experiments were conducted using the following protocol:
- RCO was allowed to crack by heating to a temperature of 400 °C, at atmospheric pressure (as the experiments were carried out at atmospheric pressure) for 1-2 minutes, till head temperature drop is observed.
- the cracked RCO was distilled under a vacuum of 1 torr till 450 deg °C and 0.2 torr thereafter till 540 °C.
- the below table 2 provides outcome of mass balance of distillation of RCO cracked with said anti-cracking additive composition (RCO+ ACA- 1 ) and RCO cracked without said anticracking additive composition.
- Table 2 Mass balance of distillation as for H2S and for the anti-cracking additive composition.
- Table 3 Hot well oil analysis results The technical outcome of the cracking experiments as conducted, and the results as provided hereinabove is discussed hereinafter.
- Bromine number of the condensable(s) collected during distillation shows a significant decrease which is a direct indication of reduction in olefins.
- Sulphur speciation results indicate increase in Polyalkyl BT and polyalkyl DBT/NBT which further indicates reduced cracking of sulphur compounds.
- the Mercaptans in the condensable(s) are higher with additive as compared to the one collected without additive. This indicates that mercaptans have not cracked to H2S when the RCO is dosed with the said anti-cracking additive composition.
- the present invention also provides a process for mitigating secondary cracking of the reduced crude oil in a vacuum heater, wherein, the process comprises adding the said anticracking additive along with reduced crude oil into the vacuum heater.
- the anti-cracking additive composition as disclosed herein mitigates cracking in Reduced Crude Oil (RCO) vacuum heater and improves vacuum during vacuum distillation of RCO. Further, the said additive composition shows excellent cracking mitigation properties through a synergistic effect of the individual components.
- RCO Reduced Crude Oil
Abstract
The present invention discloses an anti-cracking additive composition for reducing the cracking in a reduced crude oil vacuum heater. The additive composition includes an H2S scavenger, an antioxidant, and a solvent. Wherein, the H2S scavenger is Zinc Oleate, the antioxidant is 2,6-Di-tert-butyl-p-cresol, and the solvent is an aromatic solvent selected from xylene. Wherein, the additive composition containing (i) 2-4 % by weight Zinc Oleate (ii) 50-70% by weight 2,6-Di-tert-butyl-p-cresol (iii) 30-50% by weight Xylene.
Description
ANTI-CRACKING ADDITIVE COMPOSITION FOR REDUCING THE CRACKING IN A REDUCED CRUDE OIL VACUUM HEATER
FIELD OF THE INVENTION:
The present invention relates to the technical field of crude oil distillation. Specifically, the present invention relates to the technical field of vacuum distillation of crude oils. More specifically, the present invention relates to the anti-cracking additive composition and use thereof in reducing the cracking in a reduced crude oil vacuum heater.
BACKGROUND OF THE INVENTION:
Reduced crude oil (RCO) from atmospheric distillation tower bottom is heated up in a vacuum heater to around 390-410 °C before it is introduced into the vacuum distillation column. During the heating process, RCO is prone to cracking which can lead to issues such as generation of high hot well off gases (HWOG) and thus creating poor vacuum. The poor vacuum reduces distillate yield and leads to high SR yield & poor bitumen quality.
In a vacuum heater, cracking is majorly influenced by sulphur species present in the RCO. These sulphur species lead to H2S generation, and in turn leading to high hot well off gases. Many a times, refinery HWOG analysis shows H2S content above the acceptable amine absorber inlet limit (10 vol%). In addition, the free radicals formed during cracking can further induce chain reactions increasing lighter components. This results in lower vacuum (-740 mm Hg to -720 mm Hg) resulting in slippage of vacuum gas oil (VGO) into SR, and thus affecting bitumen quality.
To mitigate these issues, furnace coil output temperature (COT) is sometimes lowered by a couple of degrees or a turbulizing steam is adjusted which affects plant performance. Further, prior solutions also include addition of additive compositions to enhance distillate yield.
CN102071047A discloses a residual oil modifier for a coking delaying device and use thereof. The residual oil modifier has high practicality for raw material residual oil and can effectively improve the properties of residual oil, delay coking, effectively reduce coking amount and consequently improve the yield of middle-grade distillate. The said modifier is prepared from 1 to 25 percent of
antioxygen, 1 to 20 percent of oxidation and corrosion inhibitor, 1 to 25 percent of metal deactivator, 1 to 20 percent of dispersant and the balance of solvent, and by heating, uniformly stirring and cooling.
CN102888241A discloses an aid for improving the yield of liquid oil in an oil delayed coking device and a preparation method for the aid. The aid is prepared from N,N-bis(salicylidene) propylenediamine, p-tert-butylcatechol, tetrapentaerythritol ester, octylphenol polyoxyethylene (30) ether, N,N-di-n-butyl ammonia methylbenzotriazole and a solvent. The aid is directly added into raw material residual oil, so that a phenomenon that a coking device is coked when heating a furnace pipe and the on-stream period is prolonged can be avoided, the generation amount of coke and dry gas is reduced, and the liquid oil yield is improved.
CN101899327A discloses an anti-coking agent for high-temperature equipment and preparation and application thereof. The anti-coking agent is synthesized, by the conventional method, from the following components by weight ratio: 55%-95% of polyalkenyl succinimide esters, 3%-25% of antioxidants and 2%-20% of metal deactivators, wherein an organic solvent accounts for 50% of the total materials by weight; the antioxidant is particularly one or more of 2,6-di-tert-phenol, alkyldiphenylamine, N,N'-di-sec-butyl-p-phenylenediamine, p,p'-di-iso-octyldiphenylamine, N- phenyl-alpha naphthylamine and pentaerythrite tetra[beta(3,5-di-tert-butyl-4- hydroxyphenyl)propionate] ; the metal deactivator is particularly one or more of N,N'- disalicylidene propanediamine, triazole derivatives and thiadiazole derivatives; the organic solvent is particularly aromatic solvent, diesel or solvent oil; and the polyalkenyl succinimide esters are prepared from polyalkenyl succinimide, aldehydes and polyesters. The anti-coking agent of the invention has the advantages of good anti-coking effect, high thermostability, wide applicable temperature range and corrosion resistance.
However, as earlier stated that the cracking is majorly influenced by sulphur species present in the RCO which leads to H2S generation, and in turn leading to high hot well off gases. Accordingly, it is also important to effectively reduce the H2S generation so that effective vacuum can be maintained in the vacuum heater. Accordingly, there is a need for a solution which when applied in a vacuum heater can reduce cracking/improve vacuum, increase distillate yields and quality,
mitigate corrosion and also contribute in reducing amine consumption in amine absorber for HWOG.
SUMMARY OF THE PRESENT INVENTION:
The present invention provides an anti-cracking additive composition, wherein, the additive composition includes a H2S scavenger, an antioxidant, and a solvent. Wherein, the H2S scavenger is selected from carboxylates of Fe, carboxylates of Ni, carboxylates of Co, carboxylates of Zn or a combination thereof. The antioxidant is selected from di-tert-butyl phenols, di-tert-butyl cresols, hydroquinone, pyrogallol, propylgallate, butylated hydroxylanisole or a combination thereof. The solvent is selected from an aromatic solvent.
Wherein, the H2S scavenger is carboxylates of Zn such as but not limited to Zinc Oleate. The antioxidant is di-tert-butyl cresols such as but not limited to 2,6-Di-tert-butyl-p-cresol. The solvent is an aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof.
Specifically, in the said anti-cracking additive composition, the Zinc Oleate is 2-4 % by weight, 2,6-Di-tert-butyl-p-cresol is 50-70% by weight, and the aromatic solvent is 30-50% by weight. The weight percent is based on the total weight of the additive composition
The present invention also provides a method for preparation of the said anti-cracking additive composition, wherein, the method includes mixing the Zinc Oleate and 2,6-Di-tert-butyl-p-cresol in a solvent. The solvent is an aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof. Specifically, 2-4 % by weight of the Zinc Oleate, and 50-70% by weight of 2,6-Di-tert-butyl-p-cresol are mixed in 30-50% by weight of the said aromatic solvent.
Further, the present invention also provides a process for mitigating cracking of the reduced crude oil in a vacuum heater, wherein, the process comprises adding the said anti-cracking additive composition along with reduced crude oil into the vacuum heater. Wherein, the said anti-cracking additive composition is added in a dosage range of 5 to 500 ppm.
OBJECTIVES OF THE PRESENT INVENTION:
It is the primary objective of the present invention to mitigate the cracking in a Reduced Crude Oil (RCO) vacuum heater and thus to improve the vacuum during vacuum distillation of RCO.
It is the main objective of the present invention to provide an anti-cracking additive composition which dosed along with RCO to mitigate the cracking.
It is further objective of the present invention to maintain the vacuum in the vacuum heater and to increase the distillate yield.
It is further objective of the present invention to lower the cracking of sulphur compounds and to reduce the H2S production.
It is further objective of the present invention to significantly decrease the production of hot well off gases (HWOG) in a Reduced Crude Oil (RCO) vacuum heater.
DESCRIPTION OF THE INVENTION:
For better understanding of the present invention, cracking of RCO is explained hereinafter. The cracking of RCO is a three-stage process including primary cracking, secondary cracking, and condensation of products of cracking. Primary Cracking is unavoidable as this is due to the cleavage of weakest bonds (carbon and hetero atoms) in the least volatile fraction. This will trim the heavier molecules of their non-core heterogeneous parts resulting in decrease of the heaviest fraction. However, as the core of these heavy molecules is intact, the asphaltenes content does not reduce or even increases fraction wise. This also contributes to higher boiling (SIMDIS) profile of the SR. However, the middle and lighter fractions are not affected much during this step. But their volume percentage increases due to generation of similar molecules from the cracking of heavier fraction.
Further, the secondary cracking is dominant of the two cracking processes, as the secondary cracking is not only driven by higher heats of enthalpy, but also acidic sulphur moieties generated
in situ during the primary process. This would aggravate the cracking of core part of the heavier molecules, and thus leads to the formation of gases or highly volatile distillates. Accordingly, it is necessary to control this step, by the formation of the middle distillates and limiting the formation of gases/ highly volatile distillates.
Accordingly, the present disclosure provides a novel anti-cracking additive composition which when dosed along with RCO, will reduce cracking, and improve vacuum. Thus, this increases distillate yields and quality, mitigate corrosion, and also contribute to reducing amine consumption in amine absorber for HWOG.
The additive composition as disclosed herein is specifically developed to target and to control the secondary cracking step. The said additive composition leads to the formation of the middle distillates and limits the formation of gases or highly volatile distillates.
Accordingly, the present invention provides an anti-cracking additive composition, wherein, the additive composition includes an H2S scavenger, an antioxidant, and a solvent. Wherein, the H2S scavenger is selected from carboxylates of Fe, carboxylates of Ni, carboxylates of Co, carboxylates of Zn or a combination thereof. The antioxidant is selected from di-tert-butyl phenols, di-tert-butyl cresols, hydroquinone, pyrogallol, propylgallate, butylated hydroxylanisole or a combination thereof. The solvent is selected from an aromatic solvent.
Wherein, the H2S scavenger is carboxylates of Zn such as but not limited to Zinc Oleate. The antioxidant is di-tert-butyl cresols such as but not limited to 2,6-Di-tert-butyl-p-cresol. The solvent is the aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof. Further, in an exemplary embodiment, the solvent is xylene.
Further, the present invention provides a method for preparation of the said anti-cracking additive composition, wherein, the method includes mixing an H2S scavenger, an antioxidant, and a solvent. Wherein, the H2S scavenger is selected from carboxylates of Fe, carboxylates of Ni, carboxylates of Co, carboxylates of Zn or a combination thereof. The antioxidant is selected from
di-tert-butyl phenols, di-tert-butyl cresols, hydroquinone, pyrogallol, propylgallate, butylated hydroxylanisole or a combination thereof. The solvent is selected from an aromatic solvent.
Wherein, the H2S scavenger is carboxylates of Zn such as but not limited to Zinc Oleate. The antioxidant is di-tert-butyl cresols such as but not limited to 2,6-Di-tert-butyl-p-cresol. The solvent is aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof. Further, in an exemplary embodiment, the solvent is xylene.
Specifically, 2-4 % by weight of the Zinc Oleate, and 50-70% by weight of 2,6-Di-tert-butyl-p- cresol are mixed in 30-50% by weight of the said solvent and wherein the solvent is xylene.
Specifically, the present invention provides an anti-cracking additive composition containing (i) 2-4 % by weight Zinc Oleate (ii) 50-70% by weight 2,6-Di-tert-butyl-p-cresol (iii) 30-50% by weight Xylene. The weight percent is based on the total weight of the additive composition. The said anti-cracking additive composition acts as an anti-cracking additive to mitigate cracking in a reduced crude oil vacuum heater and improve vacuum during vacuum distillation operations.
Experimental Methodology:
The cracking experiments were conducted in a Mini Pot Still equipment using Reduced Crude oils of high sulphur crudes. The cracking experiments were conducted using the following protocol:
1. RCO was allowed to crack by heating to a temperature of 400 °C, at atmospheric pressure (as the experiments were carried out at atmospheric pressure) for 1-2 minutes, till head temperature drop is observed.
2. The cracked RCO was distilled under a vacuum of 1 torr till 450 deg °C and 0.2 torr thereafter till 540 °C.
3. The above steps were repeated with adding the said additive at a dosage of 300 ppm.
Further, the parameters which were considered as indicative of the chemical performance include density, H2S, bromine number, asphaltene content, Sulphur speciation, mercaptans, and distillation profile. The results of the experiments are provided below in Table 1.
Further, the below table 2 provides outcome of mass balance of distillation of RCO cracked with said anti-cracking additive composition (RCO+ ACA- 1 ) and RCO cracked without said anticracking additive composition.
Table 3: Hot well oil analysis results
The technical outcome of the cracking experiments as conducted, and the results as provided hereinabove is discussed hereinafter.
It is observed from the above experiments that the density of hot well oil has decreased after adding the additive. This indicates presence of lighter components in the hot well oil which would have otherwise got cracked and ended up in off-gases. Accordingly, when the RCO is dosed with the said anti-cracking additive composition there is significant decrease in hot well off gases (HWOG) and thus the vacuum in the vacuum heater does not get effected which results in higher distillate yield.
Further, the Bromine number of the condensable(s) collected during distillation shows a significant decrease which is a direct indication of reduction in olefins.
From the asphaltenes analysis, it can be concluded that cracking has reduced as the asphaltenes weight % in 540+ cut has increased with additive.
Further, the Sulphur speciation results indicate increase in Polyalkyl BT and polyalkyl DBT/NBT which further indicates reduced cracking of sulphur compounds.
Further, the Mercaptans in the condensable(s) are higher with additive as compared to the one collected without additive. This indicates that mercaptans have not cracked to H2S when the RCO is dosed with the said anti-cracking additive composition.
From the distillation data it can be inferred that the lower boiling range components have decreased in the condensable(s) when the RCO is dosed with the said anti-cracking additive composition, thus, indicating that cracking has been inhibited.
From the mass balance it is observed that yield of 540+ has decreased during the distillation carried out with RCO dosed and cracked with the said anti-cracking additive composition.
Further, H2S detected during the cracking experiments without the additive was around 8 ppm. With the additive, H2S detected was in the range of 2 ppm. This indicates that cracking of Sulphur compound has decreased to a significant extent. Accordingly, the present invention also provides a process for mitigating secondary cracking of the reduced crude oil in a vacuum heater, wherein, the process comprises adding the said anticracking additive along with reduced crude oil into the vacuum heater.
Accordingly, it is concluded that the anti-cracking additive composition as disclosed herein mitigates cracking in Reduced Crude Oil (RCO) vacuum heater and improves vacuum during vacuum distillation of RCO. Further, the said additive composition shows excellent cracking mitigation properties through a synergistic effect of the individual components.
Claims
We Claim:
1. An anti-cracking additive composition, wherein, the additive composition comprises: an H2S scavenger selected from carboxylates of Fe, carboxylates of Ni, carboxylates of Co, carboxylates of Zn or a combination thereof; an antioxidant selected from di-tert-butyl phenols, di-tert-butyl cresols, hydroquinone, pyrogallol, propylgallate, butylated hydroxylanisole or a combination thereof; and a solvent, wherein the solvent is an aromatic solvent selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof.
2. The anti-cracking additive composition as claimed in claim 1 , wherein, the H2S scavenger is carboxylates of Zn.
3. The anti-cracking additive composition as claimed in claim 1 to claim 2, wherein, the H2S scavenger is Zinc Oleate.
4. The anti-cracking additive composition as claimed in claim 1 , wherein, the antioxidant is di-tert-butyl cresols.
5. The anti-cracking additive composition as claimed in claim 1 and claim 4, wherein, the antioxidant is 2,6-Di-tert-butyl-p-cresol.
6. The anti-cracking additive composition as claimed in claim 1, wherein, the aromatic solvent is xylene.
7. The anti-cracking additive composition as claimed in claims 1-6, wherein, the Zinc Oleate is 2-4 % by weight, 2,6-Di-tert-butyl-p-cresol is 50-70% by weight, and the solvent is 30- 50% by weight, the weight percent based on the total weight of the additive composition.
8. A method for preparation of the anti-cracking additive composition as claimed in claim 1, wherein, the method comprises mixing 2-4 % of an H2S scavenger selected from carboxylates of Fe, carboxylates of Ni, carboxylates of Co, carboxylates of Zn or a combination thereof and 50-70% by weight of an antioxidant selected from di-tert-butyl phenols, di-tert-butyl cresols, hydroquinone, pyrogallol, propylgallate, butylated hydroxylanisole or a combination thereof, wherein, the said mixing is carried out in 30- 50% by weight of a solvent, wherein, the solvent is an aromatic solvent. . The method as claimed in claim 8, wherein, the H2S scavenger is carboxylates of Zn, wherein, carboxylates of Zn is Zinc Oleate.
10. The method as claimed in claim 8, wherein, the antioxidant is di-tert-butyl cresols, wherein, di-tert-butyl cresols is 2,6-Di-tert-butyl-p-cresol.
11. The method as claimed in claim 8, wherein, the aromatic solvent is selected from xylene, toluene, superior kerosene oil (SKO), light diesel oil (LDO), naphtha or a combination thereof.
12. A process for mitigating cracking in a reduced crude oil vacuum heater, wherein, the process comprises adding a reduced crude oil along with the anti-cracking additive composition as claimed in claims 1-7 into the vacuum heater.
13. The process as claimed in claim 12, wherein, the anti-cracking additive composition is added in a dosage range of 5 to 500 ppm.
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