CN1090668C - Method for inhibiting ethylene cracking device from coking - Google Patents
Method for inhibiting ethylene cracking device from coking Download PDFInfo
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- CN1090668C CN1090668C CN99119353A CN99119353A CN1090668C CN 1090668 C CN1090668 C CN 1090668C CN 99119353 A CN99119353 A CN 99119353A CN 99119353 A CN99119353 A CN 99119353A CN 1090668 C CN1090668 C CN 1090668C
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- coking
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- 238000004939 coking Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000005336 cracking Methods 0.000 title claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 6
- 239000005977 Ethylene Substances 0.000 title claims description 5
- 230000002401 inhibitory effect Effects 0.000 title abstract 9
- 239000000654 additive Substances 0.000 claims abstract description 55
- 230000000996 additive effect Effects 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000010791 quenching Methods 0.000 claims abstract description 21
- 230000000171 quenching effect Effects 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000000571 coke Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 230000014509 gene expression Effects 0.000 claims description 10
- 150000003818 basic metals Chemical class 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000010504 bond cleavage reaction Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- 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 2
- 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
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 9
- 238000005120 petroleum cracking Methods 0.000 claims 1
- HZSAJDVWZRBGIF-UHFFFAOYSA-O thiamine monophosphate Chemical compound CC1=C(CCOP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N HZSAJDVWZRBGIF-UHFFFAOYSA-O 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 6
- 239000007924 injection Substances 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 2
- 150000002894 organic compounds Chemical group 0.000 abstract 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract 2
- 239000011574 phosphorus Substances 0.000 abstract 2
- 239000003921 oil Substances 0.000 description 60
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- -1 phosphino- Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- GUGWNSHJDUEHNJ-UHFFFAOYSA-N thiamine(1+) monophosphate chloride Chemical compound [Cl-].CC1=C(CCOP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N GUGWNSHJDUEHNJ-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention provides a coking inhibiting additive for inhibiting, reducing or eliminating coking of a cracking device and a coking inhibiting method using the coking inhibiting additive. The coking inhibiting additive is organic compound containing phosphorus and amine (type I) and organic compound containing sulfur, phosphorus, amine and alkali metal (II), and its dosage is 50-400 ppm relative to raw material oil. The coking inhibiting method is that the coking inhibiting additive is added into the material flow of the device at the continuous injection port at the front end of the reaction initial reaction point. The coking inhibiting additive can reduce the coking amount of furnace tube and quenching boiler by 25-90%.
Description
In petroleum hydrocarbon thermo-cracking system olefin process, cracking furnace pipe and quenching boiler are easy to coking usually, have shortened the cycle of operation of industrial installation and have reduced economic benefit.In order to prevent, reduce, to suppress or get rid of coking, people have carried out a large amount of research to the mechanism that coking forms, and have proposed to prevent, reduce, suppress or get rid of the various methods of coking, and one of them is among the additive adding raw material.
The seventies, Nalco company is studied high-temperature coking and control thereof.United States Patent (USP) 4024048 and 4042049 discloses a kind of method that reduces or get rid of hydrodesulfurization unit or catalyzer coking in succession.This method is inhibition or scale removal additive, and promptly a spot of phosphoric acid or phosphorous acid one ester or diester before hydrodesulfurization process begins, or add in the hydrogenating desulfurization logistics in hydrodesulfurization process.
The nineties, Exxon, Kellogg, Amoco, Phillipps, mechanisms such as Linde, scale removal additive has separately been carried out the amplification or the commerical test [M.Wyrostek M.Rupp PYROKATSteamcraking in coad Craking-coils Technology and Scale Demonstration1998] of different scales, [D.M.Taylor, L.LM.Allen, T.F.McCall Amoco and coking Technologya process forInhibiting coking pyrolysis furnaces April 17-21 1994], [R.E.Blown, phillips pyro co, L.E.Greenwood Phillips pyro co, G, J.CallejasPhillips pyro co, C.Berliner, The.M.W.Kellogg co TechnollogyforApplication in Ethylene Plant], [Youdong Tong ABB Lummus Globae 9thEthylene Technollogy Seminer June 14-17 1998].
Except injecting in raw material the suppressant additive, United States Patent (USP) 4962264 also discloses and applied rare earth element such as Ce, La etc. on inside pipe wall, generates the scale suppression coating, as metal protective film.
Russ P RU 2119524 discloses a series of basic metal inorganic salt has been added the scission reaction system, the catalytic gasification coking, and unique addition means is provided.
In China, in ethylene producing device, the technical study at cracking high-temperature area use coking inhibitor still is in laboratory scale at present.In order to guarantee full scale plant running period, regulate from operational condition and material choice aspect.Therefore, limit effective throughput of device to a certain extent, lost some product yields, or give up some useful raw materials, caused total economic benefit to reduce.
The inventor is at problems of the prior art, through experimental study discovery chronically, in the ethylene producing device system, add the additive that stops coking parent (Jiao Yuan) coking, the one side passivating metallic surfaces, make burnt body particle be difficult to be attached on the wall, can also divide simultaneously and defocus the body size distribution, change the form of coking body, make fine and close spheroidal graphite shape Jiao become unformed or thread Jiao, thereby be convenient to burn off and cleaning, reduced coke cleaning consumption, prolonged the life-span of equipment operation time and equipment.
Therefore, the purpose of this invention is to provide a kind of coking suppressant additive, a kind of ethylene producing device cracking furnace pipe and quenching boiler coke suppressant additive of being used for particularly is provided.
Another object of the present invention provides a kind of method of using the coking suppressant additive to suppress coking.
The coking suppressant additive that the present invention uses, a kind of is that code name CI853 is phosphorous and organic double compound (I type) amine, another kind is that code name CI954 is sulfur-bearing phosphamidon and alkali-metal organic double compound (II type).Its structure expression is respectively:
In I formula and the II formula:
R
1-R
5Represent alkyl respectively, wherein R
1, R
2And R
4Represent that respectively carbon atom is the alkyl of 1-22, preferred carbonatoms is the alkyl of 3-20, and more preferably carbonatoms is the alkyl of 5-15;
R
3And R
5Represent that respectively carbonatoms is the alkyl of 2-20, preferred carbonatoms is the alkyl of 5-18, and more preferably carbonatoms is the alkyl of 8-13;
Me is selected from least a basic metal or its combination of lithium, sodium, potassium, rubidium, caesium;
The basic metal degree of neutralization is less than the sixth of hydroxyl value in the organic double compound molecule;
The acid amides radix is at least 1/3rd of hydroxyl value in the organic double compound molecule.
The example that presses down burnt additive of the present invention comprises: for example the I type has:
[nC
4H
9PO(C
4H
9O)N(C
2H
5)
3]·[nC
4H
9PO(C
4H
9O)
2]
[CH
3PO(C
7H
15O)N(C
3H
7)
2]·[CH
3PO(C
7H
15O)
2]
[C
2H
5PO(C
5H
11O)NHC
4H
9]·[C
2H
5PO(C
5H
11O)
2]
[C
8H
17PO(C
8H
17O)N(C
2H
5)
3]·[C
8H
17PO(C
8H
17O)
2]
[C
8H
17PO (C
8H
17O) NC
4H
9O] [C
8H
17PO (C
8H
17O)
2] etc.;
The II type has:
[C
8H
17PS(C
8H
17S)N(C
2H
5)
3]·[C
8H
17PS(SK)(C
8H
17O)]
[C
5H
11PS(C
5H
11S)N(C
3H
7)
2]·[C
5H
11PS(SK)(C
5H
11O)]
[C
2H
5PS(C
5H
11S)N(C
3H
7)
2]·[C
2H
5PS(SNa)(C
5H
11O)]
[nC
4H
9PS (C
4H
9S) N (C
2H
5)
3] [nC
4H
9PS (SK) (C
4H
9O)] etc.
But of the present invention burnt additive is yellow and amber oily transparent liquid, contains phosphino-, amide group and basic metal group.The I type is a kind of organic double compound of phosphorous and amine, and the boiling range scope is 151-224 ℃; Density in the time of 20 ℃ is 0.9240; Viscosity in the time of 20 ℃ is 7.41 centistokes(cst)s; Refractive index in the time of 20 ℃ is 1.4790.The II type is a kind of Vitamin B1 Phosphate and alkali-metal organic double compound of containing, and the boiling range scope is 143-233 ℃; Density in the time of 20 ℃ is 0.9300; Viscosity in the time of 20 ℃ is 3.80 centistokes(cst)s; Refractive index in the time of 20 ℃ is 1.4991.
But of the present invention burnt additive is dissolved in organic solvent, and is instant in polar solvent.The example of these organic solvents comprises: alkanes for example, as normal hexane, normal heptane, hexanaphthene and octane-iso etc.; Ethers is as ether, butyl ether and sherwood oil etc.; Ketone is as acetone and pentanone etc.; Alcohols is as ethanol, propyl alcohol, butanols and octanol etc.; Aromatic hydrocarbons is as benzene, toluene, ethylbenzene and dimethylbenzene etc.
Additive add the implantation site, be arranged on the front end of the leap temperature (being the initial action point) of scission reaction, the mouth of pipe bore Φ at decanting point place, be generally 0.5-10mm, be preferably 1.0-8mm, more preferably 1.0-3.0mm, linear speed by total material is designed to the pore shape, and becoming parabolic angle α with logistics, its angle is the 40-50 degree, is preferably the 44-46 degree.The coking at boiler tube and quenching boiler two places can both be inhibited.
Before cracking furnace pipe fed cracking stock, elder generation fed II type additive 1-4 hour with the amount of 0.2 weight %-0.3 weight % of raw material oil mass, and then fed cracking stock.If cracking stock is to be lighter than the petroleum naphtha light hydrocarbon, then continue amount feeding II type additive with 0.02 weight % of raw material oil mass; Overweight the solar oil heavy hydrocarbon if cracking stock belongs to, then the amount with 0.02 weight % of raw material oil mass continues to feed I type additive.
Test is carried out on the simulation cracker, and the processing power of simulator is a 3Kg/h stock oil.Simulator can be simulated the working condition of industrial crack device more widely, as type pyrolyzer such as SRT-I-SRT-V, GK-V, USC, and by the association of coking kinetics, prediction full scale plant situation.The block diagram of the breaking test of simulator is shown in Fig. 1.
In Fig. 1,1 expression convection zone, 2 expression pyrolyzer radiation sections, 3 expression quenching boilers, 4 expression oil scrubbers, 5 expression stock oils, 6 expression dilution steam generations, 7 expressions add the equipment of inhibitor, 8 expression crossover points.
Fig. 2 represents that schematically inhibitor adds the angle that Inbound is become with the Flow of Goods and Materials direction.
Test petroleum naphtha, solar oil and the tail oil of used cracking stock aromatic index (BMCI) value at 9-40.Survey the burnt cycle, petroleum naphtha 10-12 hour, diesel oil and tail oil 8-10 hour.Burnt amount quantitatively after the employing running finishes, is measured coke and is changed into CO and CO
2Amount come quantitatively.Test used stock oil performance, see Table 1.Process of the test and result are as follows.
Comparative example 1
Test cracking stock solar oil BMCI value 39, proportion D
15.560.8100, simulate industrial SRT-II type pyrolyzer processing condition, 0.45 second residence time, thinning ratio 0.75,780 ℃ of coil outlet temperatures, do not add any additive that presses down, move 8 hours, at the end, recording the tube coking amount is 2235ppm (stock oil weight relatively).
Embodiment 1
Raw material and the control condition identical with comparative example 1, the I type additive 200ppm of continuous injection weight of oil in service (stock oil weight relatively) is with the 1 identical time of operation of comparative example.During rundown, recording the tube coking amount is 386ppm (stock oil weight relatively), compares with comparative example 1, and burnt amount has reduced 82.73%.
Raw material and the control condition identical with comparative example 1, continuous injection II type additive 200ppm in service (stock oil weight relatively) moves 8 hours.During rundown, recording the tube coking amount is 357ppm (stock oil weight relatively), compares with comparative example 1, and burnt amount reduces 84.02%.Comparative example 2
Industrial crack raw material petroleum naphtha BMCI value 11.19, proportion D
15.560.7260, simulate industrial SRT-III type pyrolyzer processing condition, 0.35 second residence time, 840 ℃ of coil outlet temperatures, thinning ratio 0.50, do not add any additive that presses down, move after 12 hours, record tube coking amount 281ppm (relative stock oil weight); Quenching boiler coke amount 59.0ppm (stock oil weight relatively).
Raw material and the control condition identical with comparative example 2, continuous injection II type additive 200ppm in service (stock oil weight relatively) move after 12 hours, recorded tube coking amount 218ppm (relative stock oil weight); Quenching boiler coke amount 24.ppm (stock oil weight relatively).With comparative example 2 contrasts, boiler tube reduces coking 22.42%, and quenching boiler coke reduces 59.33%.
Raw material and the control condition identical with comparative example 2, drop into before the raw material, feed the II type additive of the 0.02 weight % amount of raw material oil mass earlier, drop into cracking stock oil after 2 hours, and the continuous simultaneously II type additive 100ppm (stock oil weight relatively) that injects, after moving at 12 o'clock, recording the tube coking amount is 189ppm (stock oil weight relatively); The quenching boiler coke amount is 8.0ppm (a stock oil weight relatively).Compare with comparative example 2, the tube coking amount has reduced 32.73%; The quenching boiler coke amount has reduced 86.44%.Comparative example 3
Industrial cracking stock solar oil BMCI14.94, proportion D
15.560.8138, simulate industrial SRT-III type pyrolyzer processing condition, 0.35 second residence time, 820 ℃ of coil outlet temperatures, thinning ratio 0.75, do not add any suppressant additive, move after 8 hours, recording the tube coking amount is 109ppm (stock oil weight relatively); The quenching boiler coke amount is 27.6ppm (a stock oil weight relatively).
Embodiment 5
Raw material and the control condition identical with comparative example 3, continuous injection I type additive in service are 200ppm (stock oil weight relatively), moves after 8 hours, and recording the tube coking amount is 65Mppm (relative stock oil weight); The quenching boiler coke amount is 11ppm (a stock oil weight relatively).Compare with comparative example 3, the tube coking amount has reduced 40.36%; The quenching boiler coke amount has reduced 60.30%.
Raw material and the control condition identical with example 5, with example 4 described identical pretreatment processs, inject I type additive 200ppm (stock oil weight relatively) continuously, move after 8 hours, recording the tube coking amount is 52ppm (stock oil weight relatively), and the quenching boiler coke amount is 8.8ppm (a stock oil weight relatively).Relatively example 3 tube coking amounts have reduced 50.1%; The quenching boiler coke amount has reduced 74.85%.Comparative example 4
Industry decompression diesel oil (tail oil) BMCI9.34, proportion D
15.560.8460, simulate industrial SRT-IV type pyrolyzer processing condition, 0.30 second residence time, 823 ℃ of coil outlet temperatures, rare ratio 0.80, do not add any additive place that presses down, move 8 hours.During rundown, recording the tube coking amount is 127ppm (raw material oil mass relatively); The quenching boiler coke amount is 24ppm (a raw material oil mass relatively).
Raw material and the control condition identical with comparative example 4, continuous injection II type additive 200ppm in service (stock oil weight relatively) move after 8 hours, and recording the tube coking amount is 85ppm (relative stock oil weight); The quenching boiler coke amount is 8.0ppm (a stock oil weight relatively), compares with comparative example 4, and the tube coking amount has reduced 33.07%; The quenching boiler coke amount has reduced 66.67%.
Raw material and the control condition identical with comparative example 4, with example 4 described identical treatment processs, inject II type additive 200ppm (stock oil weight relatively) continuously, move after 8 hours, record tube coking amount 68.5ppm (stock oil weight relatively), quenching boiler coke amount 6.5ppm (stock oil weight relatively) compares with comparative example 4, and the tube coking amount has reduced 41%; The quenching boiler coke amount has reduced 82.67%.
The model of injecting additive continuously is generally relevant with the raw material composition, and I type additive is applicable to that sulphur content is higher than the 200ppm heavy distillate, and II type additive is applicable to light ends oil and the heavy secondary processing oil that sulphur content is lower.
Use the sample result of inhibitor comprehensive more as shown in table 2.
Table 1 test cracking stock rerum natura
| The performance raw material | The industry solar oil | Industrial naphthas | Industry decompression diesel oil | The test solar oil | ||
| Proportion D 15.56℃ | 0.8138 | 0.7260 | 0.8462 | 0.8224 | ||
| Molecular-weight average wt | 230 | 120 | 454 | 200 | ||
| Sulphur content (wt%) | 330 | 170 | 620 | 135 | ||
| Flow process v% ℃ | Initial boiling point | 209 | 44.5 | 375 | 130 | |
| 10 | 234 | 77 | 429 | 135 | ||
| 30 | 258 | 105 | 467 | 155 | ||
| 50 | 284 | 123 | 477 | 185 | ||
| 70 | 314 | 137 | 488 | 220 | ||
| 90 | 364 | 153 | 498 | 255 | ||
| Do | 370 | 254 | 525 | 350 | ||
| Aromatic index BMCI | 14.94 | 11.19 | 9.34 | 39.00 | ||
| Group composition wt% | Paraffinic hydrocarbons | 88.75 | 59.99 | 95.57 | 63.84 | |
| Naphthenic hydrocarbon | 34.47 | |||||
| Aromatic hydrocarbons | 11.25 | 5.64 | 4.43 | 36.16 | ||
Table 2. test-results
| The test sequence number | Raw material | Temperature of reaction ℃ | The second residence time | Thinning ratio wt/wt | The additive model | The relative raw material of additive capacity ppm | The burnt amount of effect reduces wt% | |
| Boiler tube | Boiler | |||||||
| Comparative example 1 | The test solar oil | 780 | 0.45 | 0.75 | - | 0 | 0 | |
| Example 1 | The test solar oil | 780 | 0.45 | 0.75 | The I type | Continuous 200 | 82.73 | |
| Example 2 | The test solar oil | 780 | 0.45 | 0.75 | The I type | Continuous 200 | 84.02 | |
| Comparative example 2 | Industrial naphthas | 840 | 0.35 | 0.50 | - | 0 | 0 | 0 |
| Example 3 | Industrial naphthas | 840 | 0.35 | 0.50 | The II type | Continuous 200 | 22.42 | 59.33 |
| Example 4 | Industrial naphthas | 840 | 0.35 | 0.50 | II type II type | During | 32.73 | 86.44 |
| Comparative example 3 | The industry solar oil | 820 | 0.35 | 0.75 | - | 0 | 0 | 0 |
| Example 5 | The industry solar oil | 820 | 0.35 | 0.75 | The I type | Continuous 200 | 40.36 | 60.30 |
| Example 6 | The industry solar oil | 820 | 0.35 | 0.75 | II type I type | During | 50.10 | 74.85 |
| Comparative example 4 | The industry tail oil | 823 | 0.30 | 0.80 | - | 0 | 0 | 0 |
| Example 7 | The industry tail oil | 823 | 0.30 | 0.80 | The II type | Continuous 200 | 33.07 | 66.67 |
| Example 8 | The industry tail oil | 823 | 0.30 | 0.80 | II type II type | During | 41.0 | 82.67 |
The above embodiments only are to be used for further describing the present invention, make it can understand the present invention better.Under the situation that does not deviate from spirit of the present invention, modification or improvement that those skilled in the art can make the present invention, all within the scope of the invention.Scope of the present invention proposes in the appended claims in the back.
Claims (14)
1. an inhibition, reduce or get rid of the method for petroleum cracking system ethylene unit cracking furnace pipe and quenching boiler coke, it is characterized in that being added on the described device suppressing the coking additive, described additive is that the phosphorous of I type is to contain Vitamin B1 Phosphate and alkali-metal organic double compound with amine organic double compound and/or II type, and their structure expression is respectively:
I type: the organic double compound of phosphorous and amine:
II type: sulfur-bearing phosphamidon and alkali-metal organic double compound:
In above-mentioned two formulas:
R
1, R
2And R
4Be respectively the alkyl that carbonatoms is 1-22;
R
3And R
5Represent that respectively carbonatoms is the alkyl of 2-20;
Me represents to be selected from least a basic metal of lithium, sodium, potassium, rubidium or caesium;
The basic metal degree of neutralization is less than the sixth of hydroxyl value in the organic double compound molecule;
The acid amides radix is at least 1/3rd of hydroxyl value in the organic double compound molecule.
2. by the described method of claim 1, it is characterized in that pressing down R in the burnt additive
1, R
2And R
4Representing carbonatoms respectively is the alkyl of 3-20.
3. by the described method of claim 2, it is characterized in that pressing down R in the burnt additive
1, R
2And R
4Representing carbonatoms respectively is the alkyl of 5-10.
4. by the described method of claim 1, it is characterized in that pressing down R in the burnt additive
3And R
5Representing carbonatoms respectively is the alkyl of 5-18.
5. by the described method of claim 4, it is characterized in that pressing down R in the burnt additive
3And R
5Representing carbonatoms respectively is the alkyl of 8-13.
6. by the described method of claim 1, it is characterized in that pressing down burnt additive and be selected from [nC
4H
9PO (C
4H
9O) N (C
2H
5)
3] [nC
4H
9PO (C
4H
9O)
2], [CH
3PO (C
7H
15O) N (C
3H
7)
2] .[CH
3PO (C
7H
15O)
2], [C
2H
5PO (C
5H
11O) NHC
4H
9] [C
2H
5PO (C
5H
11O)
2], [C
8H
17PO (C
8H
17O) N (C
2H
5)
3] [C
8H
17PO (C
8H
17O)
2], [C
8H
17PO (C
8H
17O) NC
4H
9O] [C
8H
17PO (C
8H
17O)
2], [C
8H
17PS (C
8H
17S) N (C
2H
5)
3] [C
8H
17PS (SK) (C
8H
17O)], [C
5H
11PS (C
5H
11S) N (C
3H
7)
2] [C
5H
11PS (SK) (C
5H
11O)], [C
2H
5PS (C
5H
11S) N (C
3H
7)
2] [C
2H
5PS (SNa) (C
5H
11O)], [nC
4H
9PS (C
4H
9S) N (C
2H
5)
3] [nC
4H
9PS (SK) (C
4H
9O)] at least a in.
7. by the described method of claim 1, it is characterized in that pressing down burnt additive and after being dissolved in organic solvent, add.
8. by the described method of claim 7, it is characterized in that organic solvent is selected from least a in alkanes, ethers, ketone, alcohols, the aromatic hydrocarbons.
9. by the described method of claim 1, it is characterized in that I type and/or II type press down burnt additive in cracker adding in service.
10. by the described method of claim 1, it is characterized in that before the scission reaction pipe drops into cracking stock, the II type is pressed down burnt additive fed the 1-4 of system hour, after feeding cracking stock, be accompanied by material feeding I type or II type and press down burnt additive.
11. by the described method of claim 1, it is characterized in that pressing down burnt additive is to add at the continuous inlet that presses down burnt additive that is arranged on reaction initial action point front end.
12. by the described method of claim 1, it is characterized in that pressing down burnt additive is to add with the linear velocity identical with the material that adds point.
13. by the described method of claim 1, it is characterized in that the amount of relative cracking stock, adding the amount that presses down burnt additive is 50ppm-400ppm.
14. by the described method of claim 1, it is characterized in that pressing down burnt additive, to be used for gaseous alkanes, petroleum naphtha, solar oil or decompression diesel oil be the cracking system of raw material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119353A CN1090668C (en) | 1999-09-10 | 1999-09-10 | Method for inhibiting ethylene cracking device from coking |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119353A CN1090668C (en) | 1999-09-10 | 1999-09-10 | Method for inhibiting ethylene cracking device from coking |
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| CN1247887A CN1247887A (en) | 2000-03-22 |
| CN1090668C true CN1090668C (en) | 2002-09-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7425259B2 (en) * | 2004-03-09 | 2008-09-16 | Baker Hughes Incorporated | Method for improving liquid yield during thermal cracking of hydrocarbons |
| CN1305786C (en) * | 2004-08-13 | 2007-03-21 | 北京斯伯乐科学技术研究院 | Antisludging agent used in cracking gas compressor in an ethylene apparatus and its using method |
| CN100352899C (en) * | 2005-10-11 | 2007-12-05 | 杭州市化工研究院有限公司 | Ethene compressor cleaning media |
| CN101161785B (en) * | 2006-10-12 | 2011-06-15 | 中国石油化工股份有限公司 | Method for suppressing coking and carbonizing for hydrocarbons steam cracking unit |
| CN101294100B (en) * | 2007-04-28 | 2012-05-30 | 中国石油化工股份有限公司 | Method for inhibiting hydrocarbons steam cracking furnace from coking |
| CN101318872B (en) * | 2008-07-22 | 2010-12-15 | 北京斯伯乐科学技术研究院 | Ethylene cracking furnace coking restrainer and its use method |
| CN104560106A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Inhibitor and device for slowing down coking of ethylene cracking furnace pipe, and application method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962264A (en) * | 1989-10-23 | 1990-10-09 | Betz Laboratories, Inc. | Methods for retarding coke formation during pyrolytic hydrocarbon processing |
| CN1157006A (en) * | 1994-09-05 | 1997-08-13 | 国际壳牌研究有限公司 | Process for thermal cracking of residual hydrocarbon oil |
| CN1218095A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Coking and scaling inhibitor and preparation and use thereof |
-
1999
- 1999-09-10 CN CN99119353A patent/CN1090668C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962264A (en) * | 1989-10-23 | 1990-10-09 | Betz Laboratories, Inc. | Methods for retarding coke formation during pyrolytic hydrocarbon processing |
| CN1157006A (en) * | 1994-09-05 | 1997-08-13 | 国际壳牌研究有限公司 | Process for thermal cracking of residual hydrocarbon oil |
| CN1218095A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Coking and scaling inhibitor and preparation and use thereof |
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|---|---|
| CN1247887A (en) | 2000-03-22 |
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