CN1928021A - Auxiliary agent capable of improving delayed coking liquid yield, preparation method and application thereof - Google Patents
Auxiliary agent capable of improving delayed coking liquid yield, preparation method and application thereof Download PDFInfo
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- CN1928021A CN1928021A CN 200610106994 CN200610106994A CN1928021A CN 1928021 A CN1928021 A CN 1928021A CN 200610106994 CN200610106994 CN 200610106994 CN 200610106994 A CN200610106994 A CN 200610106994A CN 1928021 A CN1928021 A CN 1928021A
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- Prior art keywords
- auxiliary agent
- alkyl
- coking
- fatty alcohol
- solvent
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- Granted
Links
- 238000004939 coking Methods 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 47
- 230000003111 delayed effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 title claims description 45
- 239000000571 coke Substances 0.000 claims abstract description 24
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 16
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- -1 alkyl nitrate Chemical compound 0.000 claims abstract description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 8
- 239000003502 gasoline Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- QQHZPQUHCAKSOL-UHFFFAOYSA-N butyl nitrate Chemical compound CCCCO[N+]([O-])=O QQHZPQUHCAKSOL-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Coke Industry (AREA)
Abstract
The present invention discloses one kind of assistant for raising the yield of delayed coking liquid and its preparation process and application. The assistant consists of alkyl nitrate 20-40 wt%, fatty alcohol 10-30 wt%, dimethyl polysiloxane 10-20 wt% and solvent for the rest. The present invention can raise the yield of delayed coking liquid and reduce the yield of coke obviously.
Description
Technical field
The invention belongs to the oil refining additive agent field, particularly a kind of auxiliary agent that improves the delayed coking liquid yield and its production and application.
Background technology
Delayed coking is a kind of heat processing technique that the thermally splitting of the residual oil degree of depth is converted into gas, light, middle matter distillate and coke, characteristics such as it is low, easy to operate because of the maturation that possesses skills, construction investment, the device flexibility ratio is big, and become a kind of Heavy Oil Processing Technology of widespread use.The working ability of existing delayed coking unit has surpassed more than 60% of the total working ability of residual oil in the world, and in China, delayed coking becomes the refinery especially and handles one of conventional means of residual oil.Its typical process is: crude oil is through after the preheating, be introduced into the separation column bottom, coking oil gas contact heat-exchanging in tower of coming with the coking cat head, enter again and enter coke drum generation heat cracking reaction after the process furnace radiation section is heated to coking temperature, coking oil gas distillates from the coke cat head and enters separation column, tell cooking gas, gasoline, diesel oil and wax oil, turning oil carries out pyrogenic reaction again with raw material at the bottom of the tower.The coke that coking generates is stayed in the coke drum, discharges in tower by hydraulic decoking.
Delay coking process liquid yield (is reference point with the delayed coking fresh feed) generally has only 70%, can only reach 50%～60% during the processing poor residuum, and coke yield can reach 30%, and coke value is low, and high-sulfur Jiao is difficult to use especially.Therefore, each major oil companies of the world are carrying out the improvement of delayed coking technology always, are major objective with raising liquid yield, reduction coke yield especially.The technical measures of the raising delayed coking liquid yield that occurs have at present: add heavy aromatics or heavy virtue oil in the coking charging; Add hydrogen-rich gas and catalytic slurry; Operation conditions optimization; Change technical process etc.More external in recent years oil companies such as Exxon-Mobil company propose to add minor amounts of additives to increase the coking liquid yield in the heat scission reaction process, receive unusual effect.
The research starting that delayed coking is increased liquor abroad early, patent US 4,378,288 disclose a kind of in coking filling free radical terminator such as quinhydrones, N-phenyl-2-α amine increase liquid yield, its mechanism is that free radical terminator can stop some micromolecular compounds to form macromolecular cpd and even coke by Raolical polymerizable, thereby increases liquid yield.Patent US 4,784,744 disclose a kind of to coking a kind of free radical intermediate of annotating, promptly add a kind of hydro carbons such as methane, ethane etc., make it under the condition of catalyzer and heat, form alkyl diradical, the living radical effect that alkyl diradical and the thermally splitting of heavy oil hydrocarbon produce forms deactivated hydro carbons or stable liquid hydrocarbon, forms coke thereby suppress living radical generation condensation reaction, reduces liquid yield.Patent US5006223 discloses an amount of polyethers radical initiator of filling in coking, as polymethylene carbonyl naphthalene, poly-dimethylene naphthalene or poly-methyl carbonyl benzene, and pyrogenic reaction is carried out under lower temperature condition, can be obtained the transformation efficiency of higher coking transformation efficiency and purpose product.Patent US4298455 discloses annotate radical initiator (as Diisopropyl azodicarboxylate, benzoyl peroxide) and chain-transfer agent (as CCl in the viscosity breaking process
4), the free radical that the reaction of initiator and chain-transfer agent generates and long molecule chain hydrocarbon are competed avoiding forming coke, thereby have increased liquid yield.
Also began the research that delayed coking increases the liquor aspect in domestic nearly 2 years, patent CN1560198A discloses additive of a kind of delayed coking unit yield of light oil and preparation method thereof, this additive is mainly by 10～20 parts lytic activity material, 30～40 parts radical chain reaction inhibitor, 20～30 parts oxidation inhibitor, 10～20 parts solvent composition.Patent CN1583960A discloses a kind of mink cell focus delayed coking cracking activating additive and preparation method thereof, by weight its main component 20～40% lanthanide rare organic compound are arranged, 5～15% metal passivators, 5～15% dispersion agents, 10～30% polymeric surface active agents.In addition, patent ZL02139673.6 discloses and has added a kind of lower boiling evaporation agent to shorten the residence time of distillate in coke drum in coking, reduce the chance that the further condensation of second pyrolysis and hydrocarbon molecules generates coke, receive to improve liquid, thinner can be coker gasoline, hydrogenation coker gasoline, organic alcohol, carburet hydrogen etc., and filling rate is 2～10% of an inlet amount.
Taking a broad view of at present existing coking increases liquid receipts technology, and the problem that the auxiliary agent of being touched upon exists mainly contains:
(1) use initiator as the raw material such as Diisopropyl azodicarboxylate, the benzoyl peroxide etc. that increase liquor, cost an arm and a leg, and production, accumulating have certain danger.
(2) present, it is general only from one side mechanism that external coking increases liquor, or from free radical triggering mechanism, or from stoping coke formation mechanism, function singleness.The domestic liquor that increases increases the liquid receipts from multi-angle, but raw materials cost is higher, has influenced the economic benefit of auxiliary agent.
(3) method of employing filling thinner, filling rate is excessive, and cost is too high.
Summary of the invention
The mechanism of action that The present invention be directed to prior art increase liquid yield auxiliary agent is single, the raw materials cost height, shortcoming such as filling rate is big, and a kind of new auxiliary agent that is used to improve the delayed coking liquid yield is proposed, to improve the yield of delayed coking liquid, reduce coking yield.The present invention also provides the preparation method and the application of this auxiliary agent in addition.
Increase liquid yield auxiliary agent provided by the invention is made up of following component:
Alkyl nitric ether 20～40 weight %
Fatty Alcohol(C12-C14 and C12-C18) 10～30 weight %
Dimethyl polysiloxane 10～20 weight %
The solvent surplus
Wherein, the structural formula of described alkyl nitric ether is R-NO
3, R is C
2～C
10Alkyl, C preferably
4～C
8Alkyl; Described Fatty Alcohol(C12-C14 and C12-C18) is C
10～C
20Fatty Alcohol(C12-C14 and C12-C18), C preferably
16～C
20Fatty Alcohol(C12-C14 and C12-C18); Kinematic viscosity during 40 ℃ of described dimethyl polysiloxanes is 10000mm
2/ S～100000mm
2/ S is preferably 60000mm
2/ S～100000mm
2/ S.
Solvent of the present invention is gasoline, kerosene or solvent oil, preferred gasoline, and as straight-run spirit, catalytic gasoline or coker gasoline, hydrogenation coker gasoline preferably.
The preparation method who increases liquid receipts auxiliary agent provided by the invention is: in proportion alkyl nitric ether, organic alcohol, dimethyl polysiloxane and solvent are mixed, stirred under normal temperature, normal pressure 30～40 minutes, promptly get auxiliary agent of the present invention.
The liquid receipts auxiliary agent that increases of the present invention is used for delayed coking unit, its application method is: in outlet of coker furnace radiation section or coke drum ingress, auxiliary agent is joined in the coking raw material, add-on is that to make the content of auxiliary agent in the coking raw material be 50～300 μ g/g, preferably 100～200 μ g/g.
Delayed coking raw material of the present invention comprises the raw materials such as long residuum, vacuum residuum, visbreaking residue, catalytically cracked oil, hydrocracking tail oil and ethylene bottom oil of any crude oil.
Auxiliary agent provided by the present invention increases liquid from multiple mechanism and receives, (1) chain initiation mechanism: after auxiliary agent of the present invention joins coking raw material, can in pyrogenic reaction, promote the formation of living radical, thereby quicken to cause the free radical scission reaction of hydro carbons, make heavy feed stock change into light-end products as much as possible; (2) colloidal structure mechanism: because residual oil is made up of the complex construction unit that supramolecular structure nuclear and solvent layer form, supramolecular structure endorse with absorption or dissolve a part of molecule less, etc. the lower hydro carbons of homogenization degree, and this patent auxiliary agent can reduce the thickness of supramolecular structure nuclear and solvated layer, the low molecular hydrocarbon class of its absorption is discharged, reach the purpose that improves yield of light oil.(3) surface tension mechanism: this patent auxiliary agent can reduce the partial surface tension of the last liquid film of bubble, causes bubble to break thereby destroy firm liquid film, makes gas evolution, thereby improves yield of light oil.In sum, auxiliary agent of the present invention compared with prior art can obviously improve the yield of delayed coking liquid product; Secondly auxiliary agent provided by the invention compared with prior art has characteristics such as raw material is easy to get, the preparation of auxiliary agent is simple, filling rate is little.
Embodiment
Describe the present invention in detail with specific embodiment below, but embodiment does not limit the scope of the invention.
Embodiment 1:
(kinematic viscosity is 70000mm 40 ℃ the time to take by weighing 30g nitric acid butyl ester, 20g cetyl alcohol, 10g dimethyl polysiloxane
2/ S), 40g straight-run spirit places container, stirs at normal temperatures until mixing, obtain increasing liquid and receive the auxiliary agent A sample.
Embodiment 2:
(kinematic viscosity is 100000mm 40 ℃ the time to take by weighing 40g nitric acid n-octyl, 20g Stearyl alcohol, 10g dimethyl polysiloxane
2/ S), the 30g catalytic gasoline places container, stirs at normal temperatures until mixing, obtain increasing liquid and receive the auxiliary agent B sample.
Embodiment 3:
(kinematic viscosity is 100000mm 40 ℃ the time to take by weighing 20g butyl nitrite, 20g eicosanol, 15g dimethyl polysiloxane
2/ S), the 45g aromatic solvent naphtha places container, stirs at normal temperatures until mixing, obtain increasing liquid and receive auxiliary agent C sample.
Embodiment 4:
(kinematic viscosity is 100000mm 40 ℃ the time to take by weighing 30g nitroethane, 25g eicosanol, 20g dimethyl polysiloxane
2/ S), 25g hydrogenation coker gasoline places container, stirs at normal temperatures until mixing, obtain increasing liquid and receive auxiliary agent D sample.
Embodiment 5:
(kinematic viscosity is 100000mm 40 ℃ the time to take by weighing 25g oil of mirbane, 30g eicosanol, 15g dimethyl polysiloxane
2/ S), 30g hydrogenation coker gasoline places container, stirs at normal temperatures until mixing, obtain increasing liquid and receive auxiliary agent E sample.
Embodiment 6:
Present embodiment is the lab scale of auxiliary agent.At first then 100g residual oil is added in the special beaker, add 200 μ g/g auxiliary agents then and mix, again beaker is put into reactor, reactor places process furnace, and behind nitrogen replacement reactor three times, furnace temp is preset to 500 ℃.Pressure in the process reactor that raw material heats up raises gradually, and along with the rising of temperature, what pressure raise speeds up, when pressure is elevated to 1.2Mpa, the record temperature of reactor, open water coolant and reactive system baiting valve, pressure sharply descends, temperature of reactor continues to raise, reaction oil gas constantly enters watercooler from reactor, enter the receipts liquid bottle that places the frozen water cooling tank afterwards, and the splitting gas that reaction produces is from receiving the top emptying of liquid bottle, product liquid closes in the liquid bottle, and coke constantly is accumulated in the beaker.Stop experiment when reactionless oil gas distillates, respectively product liquid and coke are weighed, calculate product liquid and coking yield, product liquid liquor charging analysis of hplc is formed.Lab scale the results are shown in Table 1.
The little test result of table 1
| Project | Blank | The A sample | The B sample | The C sample | The D sample | The E sample | |
| 1.2Mpa the time temperature of reaction, ℃ | 423 | 418 | 417 | 416 | 415 | 417 | |
| Liquid yield % | 70.04 | 71.12 | 73.07 | 72.16 | 72.65 | 71.63 | |
| Coke yield % | 21.32 | 20.73 | 19.74 | 20.26 | 20.14 | 20.52 | |
| Liquid is formed % | Gasoline | 17.9 | 18.3 | 20.4 | 19.6 | 20.1 | 18.8 |
| Diesel oil | 31.4 | 32.8 | 34.3 | 33.7 | 33.7 | 33.1 | |
| Heavy oil | 50.7 | 48.9 | 45.3 | 47.4 | 46.3 | 48.1 | |
From little test result as can be seen the isooctyl ester nitrate effect be better than the nitric acid butyl ester, the long-acting more fruit of Fatty Alcohol(C12-C14 and C12-C18) carbochain is good more, the big more effect of dimethyl polysiloxane viscosity is good more, active principle increases, effect improves.
Embodiment 7:
Present embodiment is the pilot scale of auxiliary agent, the technology boiling range of pilot plant is: stock oil is extracted out from head tank through toothed gear pump, mix with the water vapour that comes from vapour generator, be pumped to the process furnace preheating section together and be preheated to 420 ℃, be heated to 490 ℃ of temperature of reaction through process furnace again, with enter coke drum after auxiliary agent mixes and carry out cracking reaction, reaction oil gas passes through one-level drainer, B-grade condensation jar and cold well respectively, liquid product is collected in drainer and the receiving tank, gas is emptying after sampling, coke cleaning after the off-test.Auxiliary agent is annotated the plug pump with trace after with an amount of solvent cut it is filled in the raw material, and decanting point is at the source line place of coke drum, and adding dosage is 160 μ g/g.The recycle ratio of pilot plant is 0.3, and stock oil consists of 3 parts of vacuum residuum and mixes oil at the bottom of 5 parts of towers, mixing raw material oil nature analysis in table 2.The main operational condition of medium-sized test sees Table 3.
Table 2 stock oil character
| Project | Data |
| Density (20 ℃)/kgm -3Viscosity (80 ℃)/mm 2·s -1Carbon residue/w% throw out w% S/ μ gg -1 N/μg·g -1Metal Fe/ μ gg -1 Ni/μg·g -1 Ca/μg·g -1Group composition/w% saturated hydrocarbons aromatic hydrocarbons colloid+asphalitine boiling range/℃ IBP 5% 10% 20% 30% | 960.3 313.6 12.16 0.0078 4115 5795 14.15 55.63 9.31 25.925 38.26 35.8 277.4 378.5 405.1 452.5 514.3 |
The main operational condition of table 3 medium-sized tester
| Project | Operational condition |
| Inlet amount, kgh -1Water injection rate, m% furnace outlet temperature, ℃ coking tower column bottom temperature, ℃ coking tower tower top pressure, kg recycle ratio experimental period, h | 2.30 6.5 450 490 3.3 0.3 15 |
Product distribution blank and that add after agent is tested sees Table 4, and liquid product obtains gasoline fraction, diesel oil distillate and wax oil cut through normal pressure distillation and underpressure distillation, and the comparing result that liquid yield and product distribute sees Table 5.
Table 4 product blank and that add the agent test distributes
| Project | Blank | The A sample | The B sample | The C sample | The D sample | The E sample |
| Coke yield, m% | 26.48 | 25.83 | 24.85 | 25.37 | 25.22 | 25.52 |
| Gas recovery ratio, % | 10.21 | 9.82 | 8.68 | 9.29 | 8.82 | 9.27 |
| Total liquid yield, % | 63.29 | 64.32 | 66.45 | 65.31 | 65.93 | 65.17 |
| Loss, % | 0.02 | 0.03 | 0.02 | 0.03 | 0.03 | 0.04 |
The comparing result that table 5 liquid yield and product distribute
| Project | The A sample | The B sample | The C sample | The D sample | The E sample |
| Liquid yield, % | ↑1.03 | ↑3.16 | ↑2.02 | ↑2.64 | ↑1.88 |
| ～170 ℃ (gasoline) | ↑0.23 | ↑0.46 | ↑0.24 | ↑0.33 | ↑0.28 |
| 170 ℃～350 ℃ (diesel oil) | ↑0.53 | ↑1.52 | ↑0.93 | ↑1.23 | ↑1.07 |
| 350 ℃～460 ℃ (wax oil) | ↑0.27 | ↑1.18 | ↑0.85 | ↑1.08 | ↑0.53 |
From table data as can be seen, pilot-scale experiment is consistent with the lab scale result, the isooctyl ester nitrate effect is better than the nitric acid butyl ester, the long-acting more fruit of Fatty Alcohol(C12-C14 and C12-C18) carbochain is good more, the big more effect of dimethyl polysiloxane viscosity is good more, the active principle increase increases liquid effect raising.And the delayed coking that provides of this patent increases liquor as can be seen can increase liquid yield 1～3%, and mainly increases diesel oil and wax oil cut.
Claims (9)
1. one kind is improved delayed coking liquid yield auxiliary agent, it is characterized in that this auxiliary agent is made up of following component:
Alkyl nitric ether 20～40 weight %
Fatty Alcohol(C12-C14 and C12-C18) 10～30 weight %
Dimethyl polysiloxane 10～20 weight %
The solvent surplus
Wherein the structural formula of alkyl nitric ether is R-NO
3, R is C
2～C
10Alkyl; Fatty Alcohol(C12-C14 and C12-C18) is C
10～C
20Fatty Alcohol(C12-C14 and C12-C18); Kinematic viscosity was 10000mm when dimethyl polysiloxane was 40 ℃
2/ S～100000mm
2The dimethyl polysiloxane of/S.
2. auxiliary agent according to claim 1 is characterized in that: described Fatty Alcohol(C12-C14 and C12-C18) is C
16～C
20Fatty Alcohol(C12-C14 and C12-C18).
3. auxiliary agent according to claim 1 is characterized in that: the kinematic viscosity during 40 ℃ of described dimethyl polysiloxanes is 60000mm
2/ S～100000mm
2/ S.
4. auxiliary agent according to claim 1 is characterized in that: the alkyl R in the described alkyl nitric ether is C
4～C
8Alkyl.
5. auxiliary agent according to claim 1 is characterized in that: described solvent is gasoline, kerosene or solvent oil.
6. auxiliary agent according to claim 5 is characterized in that: described solvent is a gasoline.
7. the preparation method of the described auxiliary agent of claim 1, the step that it is characterized in that this method is: in proportion alkyl nitric ether, organic alcohol, dimethyl polysiloxane and solvent are joined in the container, under normal temperature, normal pressure, stirred 30～40 minutes, and promptly got auxiliary agent of the present invention.
8. the application of the described auxiliary agent of claim 1, it is characterized in that: auxiliary agent is used for delayed coking unit, its application method is in outlet of coker furnace radiation section or coke drum ingress, auxiliary agent is joined in the coking raw material, and add-on is that to make the content of auxiliary agent in the coking raw material be 50～300 μ g/g.
9. application according to claim 8 is characterized in that: the add-on of described auxiliary agent is 100～200 μ g/g.
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| CNB2006101069940A CN100387686C (en) | 2006-09-06 | 2006-09-06 | Auxiliary agent capable of improving delayed coking liquid yield, preparation method and application thereof |
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|---|---|---|---|
| CNB2006101069940A CN100387686C (en) | 2006-09-06 | 2006-09-06 | Auxiliary agent capable of improving delayed coking liquid yield, preparation method and application thereof |
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| CN100387686C CN100387686C (en) | 2008-05-14 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113367B (en) * | 2007-07-19 | 2010-11-10 | 茂名学院 | Adding substance for reducing furnace tube deposition coking and improving liquid yield of delayed coker |
| CN102311757A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Method for improving yield of delayed coking liquid product |
| CN102311756A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Addition agent for thermal inversion process of heavy oil and preparation method of addition agent |
| CN103768831A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | High temperature stable defoaming agent and application thereof in delay coking |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4784744A (en) * | 1987-09-10 | 1988-11-15 | Mobil Oil Corporation | Process for stabilizing intermediates and improving liquid yields and coke quality |
| CN1219022C (en) * | 2003-05-31 | 2005-09-14 | 中国石油化工股份有限公司 | Delayed coking method for increasing light oil yield |
-
2006
- 2006-09-06 CN CNB2006101069940A patent/CN100387686C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113367B (en) * | 2007-07-19 | 2010-11-10 | 茂名学院 | Adding substance for reducing furnace tube deposition coking and improving liquid yield of delayed coker |
| CN102311757A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Method for improving yield of delayed coking liquid product |
| CN102311756A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Addition agent for thermal inversion process of heavy oil and preparation method of addition agent |
| CN102311757B (en) * | 2010-06-29 | 2013-11-06 | 中国石油化工股份有限公司 | Method for improving yield of delayed coking liquid product |
| CN102311756B (en) * | 2010-06-29 | 2013-11-27 | 中国石油化工股份有限公司 | Addition agent for thermal inversion process of heavy oil and preparation method of addition agent |
| CN103768831A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | High temperature stable defoaming agent and application thereof in delay coking |
| CN103768831B (en) * | 2012-10-24 | 2015-05-13 | 中国石油化工股份有限公司 | High temperature stable defoaming agent and application thereof in delay coking |
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|---|---|
| CN100387686C (en) | 2008-05-14 |
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