CN115305118B - Coke inhibiting and income increasing agent and preparation method thereof - Google Patents
Coke inhibiting and income increasing agent and preparation method thereof Download PDFInfo
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- CN115305118B CN115305118B CN202110502549.0A CN202110502549A CN115305118B CN 115305118 B CN115305118 B CN 115305118B CN 202110502549 A CN202110502549 A CN 202110502549A CN 115305118 B CN115305118 B CN 115305118B
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- polyoxyethylene ether
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- sulfonate
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 78
- 239000000571 coke Substances 0.000 title claims abstract description 74
- 230000002401 inhibitory effect Effects 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 88
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 88
- 230000005764 inhibitory process Effects 0.000 claims abstract description 55
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 37
- 239000010452 phosphate Substances 0.000 claims abstract description 37
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- -1 polyoxyethylene Polymers 0.000 claims abstract description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 19
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 18
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 150000004665 fatty acids Chemical group 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 2
- 230000000638 stimulation Effects 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 32
- 230000000694 effects Effects 0.000 abstract description 16
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000001804 emulsifying effect Effects 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 45
- 238000004939 coking Methods 0.000 description 17
- 150000003254 radicals Chemical class 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 230000002195 synergetic effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 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 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 8
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 7
- UUWJHAWPCRFDHZ-UHFFFAOYSA-N 1-dodecoxydodecane;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC UUWJHAWPCRFDHZ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004227 thermal cracking Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000007348 radical reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OREKREJVUNVFJP-UHFFFAOYSA-N 2-triacontylphenol Chemical group CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O OREKREJVUNVFJP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- QKIAYRRGJHLRAQ-UHFFFAOYSA-N hexadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 QKIAYRRGJHLRAQ-UHFFFAOYSA-N 0.000 description 1
- GELUAPFKLDGNFV-UHFFFAOYSA-N hexyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCOS(=O)(=O)C1=CC=CC=C1 GELUAPFKLDGNFV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- GQCRMKIDBZVXFG-UHFFFAOYSA-N pentane;phenol Chemical group CCCCC.OC1=CC=CC=C1 GQCRMKIDBZVXFG-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
-
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a coke inhibition and income increasing agent and a preparation method thereof. The coke inhibition and income increasing agent comprises 35 to 65 parts of polyoxyethylene ether phosphate, 15 to 25 parts of alkylphenol polyoxyethylene, 10 to 20 parts of sulfonate, 5 to 10 parts of phenol and 15 to 35 parts of aromatic concentrated oil by weight. The polyoxyethylene ether bond in the polyoxyethylene ether phosphate has the characteristics of good stability to acid, alkali and salt, high temperature resistance and capability of being used in a larger temperature range. The polyoxyethylene ether phosphate ensures that the finally formed compound surfactant has stronger wettability, adsorptivity, permeability, dispersibility, emulsifying property, compatibilizer and washing effect, thereby improving the dissolving capacity of an integral dispersion system in residual oil and further improving the yield of light oil.
Description
Technical Field
The invention relates to the technical field of oil refining and yield increasing agents, in particular to a coke inhibition and yield increasing agent and a preparation method thereof.
Background
The delayed coking device is an important means for deep processing of various heavy oil products such as residual oil in a refinery, and the coking device needs to work in the following two aspects to improve the overall economic benefit of the device: firstly, ensuring the full-load long-period operation of the device; and secondly, higher liquid yield and lower coke yield are obtained through process optimization. Thus, optimizing the plant operation, adding the necessary coke-inhibiting and yield-increasing agents increases the plant distillate yield, decreases the coke yield, and extends the plant run length, all of which are the objectives sought after by delayed coker operation efforts.
The heavy oil product such as residuum is composed of complex structural units formed by a supramolecular structure core and a solvent layer, and the supramolecular structure core can adsorb or dissolve a part of hydrocarbons with smaller molecules and lower isogenization degree. The coke inhibition and yield increase agent can reduce the thickness of the supramolecular structure core and the solvation layer, so that the adsorbed low-molecular hydrocarbon is released to carry out thermal cracking reaction, and the yield of the light oil is further improved.
In addition, the polycyclic aromatic hydrocarbon generated by the raw material and the pyrolysis can generate free radical dehydrogenation condensation reaction, and the heteroatom compounds such as oxygen, sulfur, nitrogen and the like contained in the raw material can trigger free radical polymerization reaction, and the two reactions can generate macromolecular compounds, further the macromolecular compounds are subjected to dehydrogenation condensation to form colloid and asphaltene, and finally the colloid and asphaltene are condensed to form coke. The coke inhibition and yield increase agent can provide active hydrogen atoms to prevent free radical polycondensation reaction, thereby inhibiting the formation of macromolecular compounds and further inhibiting the generation of coke.
Therefore, the coke inhibition and yield increase agent can improve the yield of the distillate oil, and mainly because the coke inhibition and yield increase agent changes the characteristic parameters of a heavy component dispersion system on one hand, improves the dissolution capacity of a dispersion medium and achieves the aim of increasing the liquid yield. Meanwhile, the coke inhibition and yield increase agent can provide active hydrogen atoms to prevent free radical condensation reaction and polymerization reaction, thereby inhibiting the generation of macromolecular compounds and even coke. The action principle of the coke inhibition and yield increase agent is primarily summarized into three mechanisms of a free radical chain reaction mechanism, a dispersion solubilization mechanism and a polymerization inhibition and coke increase mechanism.
The Chinese patent application with the patent application number of 201210285586.1 discloses a coke-preventing light oil yield-increasing agent for a delayed coking device of an oil refinery, which is formed by compounding a high-temperature-resistant antioxidant, a high-temperature-resistant detergent, a high-temperature-resistant dispersing agent, a high-temperature-resistant metal passivating agent and fatty amine polyoxyethylene ether, and has a scale inhibition effect of more than 85 percent and a total light oil yield of more than 1.5 weight percent. However, the formulation of the coke inhibition and yield increase agent is relatively complex.
The Chinese patent with patent authority publication number CN102977921B discloses a preparation method of a delayed coking anti-coking and yield-increasing agent, which is an anti-coking and yield-increasing agent compounded by alkylbenzene sulfonic acid, organic amine, alkylamide and solvent, and has high temperature resistance, oxidation resistance, scaling resistance, corrosion resistance and excellent dispersion performance. However, the reaction temperature of the preparation method is high, and the relative process is complex.
The Chinese patent application No. 201810024076.6 discloses a liquid yield increasing agent for delayed coking in oil refining process, which is a liquid yield increasing agent compounded by dispersing a decoking agent, free radical quenching, an asphaltene decomposition agent, an asphaltene cracking agent, a hydrogen supply agent, a scale inhibition and coking prevention agent, an emulsifying agent, a metal passivating agent, a corrosion inhibitor and a diluent. However, the formulation of the coke inhibition and yield increase agent is relatively complex.
The coke inhibition and yield increase agent has the advantages of inhibiting the generation of coke in oil residues and improving the yield of light oil. However, the problems of complex preparation process of the coke inhibition and yield increase agent, high energy consumption caused by high temperature in the preparation process and complex formula exist.
Disclosure of Invention
The invention mainly aims to provide a coke inhibition and income increasing agent and a preparation method thereof, which are used for solving the problem that the formulation of the coke inhibition and income increasing agent in the prior art is complex.
In order to achieve the above object, according to one aspect of the present invention, there is provided a coke inhibition and increase agent comprising, in parts by weight, 35 to 65 parts of polyoxyethylene ether phosphate, 15 to 25 parts of alkylphenol ethoxylates, 10 to 20 parts of sulfonate, 5 to 10 parts of phenol and 15 to 35 parts of aromatic concentrated oil.
Further, the polyoxyethylene ether phosphate is fatty acid polyoxyethylene ether phosphate and C 12 ～C 16 One or two of fatty alcohol polyoxyethylene ether phosphate esters.
Further, the alkylphenol ethoxylate is C 5 ～C 30 Linear alkylphenol ethoxylates of (a).
Further, the sulfonate is C 12 ～C 20 Alkyl aryl sulfonates and polyoxyethylene ether sulfonates.
Further toGround, the above C 12 ～C 20 The weight ratio of the alkylaryl sulfonate to the polyoxyethylene ether sulfonate is 2:3-6.
Further, the aromatic hydrocarbon concentrated oil is one or a mixture of two of three-wire oil extraction reduction and four-wire oil extraction reduction.
According to another aspect of the present invention, there is provided a method for preparing the aforementioned coke-inhibiting and increasing agent, comprising: step S1, stirring and mixing polyoxyethylene ether phosphate and aromatic concentrated oil for the first time to obtain a first mixed system; and S2, stirring and mixing the first mixed system with alkylphenol ethoxylates, sulfonate and phenol for the second time to obtain the coke inhibition and yield increase agent.
Further, the time of the first stirring and mixing and the time of the second stirring and mixing are respectively independent from each other and are 1 to 2.5 hours.
Further, the temperature of the first stirring and mixing and the temperature of the second stirring and mixing are respectively and independently 50-70 ℃.
Further, the stirring speeds of the first stirring and mixing and the second stirring are respectively independent and are 500-1500 r/min.
By applying the technical scheme of the invention, the polyoxyethylene ether phosphate is adopted as an activation main body, and the polyoxyethylene ether bond has the characteristics of good stability to acid, alkali and salt, high temperature resistance and capability of being used in a larger temperature range. The polyoxyethylene ether phosphate is a commonly used surfactant, has the characteristics of anions and non-ions, has good intersolubility and compatibility with other surfactants, and can be well compatible with alkylphenol polyoxyethylene ether non-ionic surfactants and sulfonate anionic surfactants so as to cooperate with the alkylphenol polyoxyethylene ether nonionic surfactants to achieve the synergistic effect of the surfactants, so that the finally formed compound surfactant has stronger wettability, adsorptivity, permeability, dispersibility, emulsifying property, compatibilization and washing effect, further improves the dissolving capacity of an integral dispersion system in residual oil, and releases low-molecular hydrocarbons adsorbed by supramolecular structure cores in the residual oil raw materials to carry out thermal cracking reaction, thereby improving the yield of light oil.
Meanwhile, the active main polyoxyethylene ether phosphate and alkylphenol polyoxyethylene ether are surfactants with active hydrogen atoms; the phenol can prevent the influence of bad substances such as oxygen and the like, helps to capture and neutralize free radicals, and can lead aromatic hydrocarbon and olefin to be difficult to polymerize into coke at high temperature by using the high-temperature chain initiation terminator, so that the free radical reaction is stopped, namely the polycondensation reaction is relatively stopped. Both the functions are beneficial to reducing the free radical condensation reaction and polymerization reaction in the residual oil raw material, thereby inhibiting the generation of macromolecular compounds, further inhibiting the formation of colloid and asphaltene by dehydrogenation condensation and reducing the probability of final condensation into coke.
The coke inhibition and yield increase agent has excellent coking inhibition effect, and polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether, sulfonate and phenol are mainly surfactants, so that the coke inhibition and yield increase agent has a simple formula and wide raw material sources, and the components have good synergistic effect, so that the use of the surfactants is reduced, and the preparation cost of the coke inhibition and yield increase agent is further reduced.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed by the background technology, the problem of complex formulation of the coke inhibition and yield increase agent exists in the prior art, and the invention provides the coke inhibition and yield increase agent and a preparation method thereof.
In a typical embodiment of the present application, a coke inhibition and stimulation agent is provided, which comprises, in parts by weight, 35-65 parts of polyoxyethylene ether phosphate, 15-25 parts of alkylphenol ethoxylates, 10-20 parts of sulfonate, 5-10 parts of phenol and 15-35 parts of aromatic concentrated oil.
The application adopts polyoxyethylene ether phosphate as an activation main body, wherein polyoxyethylene ether bonds have the characteristics of good stability to acid, alkali and salt, high temperature resistance and capability of being used in a larger temperature range. The polyoxyethylene ether phosphate is a commonly used surfactant, has the characteristics of anions and non-ions, has good intersolubility and compatibility with other surfactants, and can be well compatible with alkylphenol polyoxyethylene ether non-ionic surfactants and sulfonate anionic surfactants so as to cooperate with the alkylphenol polyoxyethylene ether nonionic surfactants to achieve the synergistic effect of the surfactants, so that the finally formed compound surfactant has stronger wettability, adsorptivity, permeability, dispersibility, emulsifying property, compatibilization and washing effect, further improves the dissolving capacity of an integral dispersion system in residual oil, and releases low-molecular hydrocarbons adsorbed by supramolecular structure cores in the residual oil raw materials to carry out thermal cracking reaction, thereby improving the yield of light oil.
Meanwhile, the active main polyoxyethylene ether phosphate and alkylphenol polyoxyethylene ether are surfactants with active hydrogen atoms; the phenol can prevent the influence of bad substances such as oxygen and the like, helps to capture and neutralize free radicals, and can lead aromatic hydrocarbon and olefin to be difficult to polymerize into coke at high temperature by using the high-temperature chain initiation terminator, so that the free radical reaction is stopped, namely the polycondensation reaction is relatively stopped. Both the functions are beneficial to reducing the free radical condensation reaction and polymerization reaction in the residual oil raw material, thereby inhibiting the generation of macromolecular compounds, further inhibiting the formation of colloid and asphaltene by dehydrogenation condensation and reducing the probability of final condensation into coke.
The coke inhibition and yield increase agent has excellent coking inhibition effect, and polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether, sulfonate and phenol are mainly surfactants, so that the coke inhibition and yield increase agent has a simple formula and wide raw material sources, and the components have good synergistic effect, so that the use of the surfactants is reduced, and the preparation cost of the coke inhibition and yield increase agent is further reduced.
In one embodiment of the present application, in order to further enhance the properties of polyoxyethylene ether phosphate esters as the active host, such as to provide a greater amount of active hydrogen atoms, to inhibit polymerization and condensation of free radicals in the residuum raw materials, and to enhance the synergistic effect of polyoxyethylene ether phosphate esters with other adjuvants (alkylphenol ethoxylates, sulfonates, and phenols), such as to increase the surfaceThe adsorption amount of the whole surfactant at the oil-water interface, thereby playing the synergistic effect of the surfactant, and the polyoxyethylene ether phosphate is preferably fatty acid polyoxyethylene ether phosphate or C 12 ～C 16 One or two of fatty alcohol polyoxyethylene ether phosphate esters. In order to further exert the excellent properties of the fatty alcohol-polyoxyethylene ether phosphate, C is preferred 12 ～C 30 Fatty alcohol polyoxyethylene ether phosphate esters of (a).
In one embodiment of the present application, the alkylphenol ethoxylate is C 5 ～C 30 The linear alkylphenol ethoxylates of (2) to further enhance the amount of active hydrogen atoms of the coke inhibition and yield enhancement agent and enhance the synergistic effect of the alkylphenol ethoxylates and other surfactants.
To further improve the high temperature and alkali resistance of the sulfonate, effectively reduce the effect of the particles as active centers of coking reaction, reduce the tendency of colloid and asphaltene to condense into coke, and preferably the sulfonate is C 12 ～C 20 Alkyl aryl sulfonates and polyoxyethylene ether sulfonates.
To further enhance the synergy of the sulfonate and other surfactants, e.g., to increase the tightness of the interfacial film of the formulated surfactant, thereby providing a synergistic effect, preferably C as described above 12 ～C 20 The weight ratio of the alkylaryl sulfonate to the polyoxyethylene ether sulfonate is 2:3-6. The sulfonate has high surface activity, easily available raw materials, simple production process, low cost and good compatibility. Wherein C is 12 ～C 20 The weight ratio of the alkylaryl sulfonate to the polyoxyethylene ether sulfonate is 2:3-6, which is more favorable for the synergy of alkylaryl and polyoxyethylene ether groups of the alkylaryl sulfonate and the polyoxyethylene ether sulfonate, so that the alkylaryl sulfonate has better hydrophilicity and lipophilicity, and further cooperates with other components in the coke inhibition and yield increase agent, and further improves the coking inhibition effect of the obtained coke inhibition and yield increase agent.
In one embodiment of the present application, the aromatic hydrocarbon concentrate is one or a mixture of two of a three-wire reduced extract and a four-wire reduced extract. The solubility and dispersion of the surfactant in the solvent are improved, so that the synergistic effect of the surfactant is promoted, the surfactant is well mixed and permeated with residual oil, and the coking inhibition effect on raw materials in the residual oil is further realized.
In another exemplary embodiment of the present application, a method for preparing a coke-inhibiting and increasing agent is provided, the method comprising: step S1, stirring and mixing polyoxyethylene ether phosphate and aromatic concentrated oil for the first time to obtain a first mixed system; and S2, stirring and mixing the first mixed system with alkylphenol ethoxylates, sulfonate and phenol for the second time to obtain the coke inhibition and yield increase agent.
According to the preparation method of the coke inhibition and income increasing agent, firstly, the polyoxyethylene ether phosphate and the aromatic hydrocarbon concentrated oil are mixed and stirred, so that the polyoxyethylene ether phosphate is fully dispersed in the aromatic hydrocarbon concentrated oil, and when alkylphenol polyoxyethylene ether, sulfonate and phenol are mixed and stirred, the polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether, sulfonate and phenol are fully mixed, permeated and dispersed, the adsorption quantity of the surfactant at an oil-water interface and the tightness degree of the compound surfactant precipitated out of an interfacial film are increased, the synergistic effect among the components is exerted, and the finally obtained coke inhibition and income increasing agent has a good coking inhibition effect on raw materials in residual oil.
In order to increase the contact property between the components in the formulation of the coke-inhibiting and yield-increasing agent and improve the synergistic effect, the time of the first stirring and mixing and the time of the second stirring and mixing are preferably 1-2.5 h respectively and independently.
In one embodiment of the present application, the temperature of the first stirring and mixing and the second stirring and mixing are respectively and independently 50-70 ℃, so as to improve the synergistic effect between the components in the formulation of the coke inhibition and yield increase agent.
The stirring is a conventional operation of mixing different substances, and in order to improve the dispersion effect of the components in the formulation of the coke inhibition and yield increase agent, the stirring speeds of the first stirring and mixing and the second stirring are preferably 500-1500 r/min respectively and independently.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Mixing and stirring 35 parts by weight of lauryl alcohol ether phosphate (APO-3P, wuhan Fuxin Yu technology Co., ltd.) in 30 parts by weight of three-wire reduced oil for 2 hours at a stirring speed of 1000r/min and a mixing temperature of 60 ℃ to obtain a first mixed system; and mixing and stirring the first mixed system with 25 parts of nonylphenol polyoxyethylene ether (emulsifier TX series, jiangsu Jiafeng chemical Co., ltd.), 20 parts of a mixture of sodium dodecyl benzene sulfonate and sodium polyoxyethylene ether sulfonate (Jinan Qilida chemical Co., ltd.) and 10 parts of phenol for 2 hours at the stirring speed of 1000r/min and the mixing temperature of 60 ℃, wherein the weight ratio of the alkylaryl sulfonate to the polyoxyethylene ether sulfonate is 1:2, and obtaining the scorch inhibiting and income increasing agent A.
Example 2
Example 2 differs from example 1 in that 65 parts of lauryl ether phosphate, 25 parts of three-wire reduced oil, 15 parts of nonylphenol polyoxyethylene ether, 10 parts of a mixture of sodium dodecyl phenyl sulfonate and sodium polyoxyethylene ether sulfonate, and 5 parts of phenol are taken in example 2 to obtain a scorch inhibiting and income increasing agent B.
Example 3
Example 3 differs from example 1 in that 65 parts of lauryl ether phosphate, 15 parts of three-wire reduced oil, 20 parts of nonylphenol polyoxyethylene ether, 12 parts of a mixture of sodium dodecyl phenyl sulfonate and sodium polyoxyethylene ether sulfonate, and 8 parts of phenol are taken in example 2 to obtain a scorch retarder and an income increasing agent C.
Example 4
Example 4 differs from example 1 in that 45 parts of lauryl ether phosphate, 35 parts of three-wire reduced oil, 15 parts of nonylphenol polyoxyethylene ether, 15 parts of a mixture of sodium dodecyl phenyl sulfonate and sodium polyoxyethylene ether sulfonate, and 10 parts of phenol are taken in example 2 to obtain a scorch inhibiting and income increasing agent D.
Example 5
Example 5 differs from example 1 in that the weight ratio of sodium dodecylphenylsulfonate to sodium polyoxyethylene ether sulfonate in example 5 is 2:3, and a coke-inhibiting and yield-increasing agent E is obtained.
Example 6
Example 6 differs from example 1 in that the weight ratio of sodium dodecylphenylsulfonate to sodium polyoxyethylene ether sulfonate in example 6 is 1:3, and a coke-inhibiting and yield-increasing agent F is obtained.
Example 7
Example 7 differs from example 1 in that the weight ratio of sodium dodecylphenylsulfonate to sodium polyoxyethylene ether sulfonate in example 7 is 1:1, and a coke-inhibiting and yield-increasing agent G is obtained.
Example 8
Example 8 differs from example 1 in that the polyoxyethylene ether phosphate in example 8 is n-dodecyl polyoxyethylene ether phosphate (Zhejiang biosciences Co., ltd.), the rotation speed of the first stirring and the second stirring is 500r/min, and the mixing temperature of the first and the second stirring is 50 ℃, so as to obtain the scorch inhibiting and increasing agent H.
Example 9
Example 9 differs from example 1 in that the polyoxyethylene ether phosphate in example 9 is a polyoxyethylene fatty acid ether phosphate of cetyl alcohol (Hubei Xin Ming Tai chemical Co., ltd.), a mixture of polyoxyethylene fatty acid ether phosphate, and the rotational speed of the first stirring and the second stirring is 1500r/min, and the temperature of the first and the second mixing is 70 ℃, thereby obtaining the scorch retarder I.
Example 10
Example 10 differs from example 1 in that the rotational speed of the first stirring and the second stirring in example 10 is 400r/min, and the temperature of the first and the second mixing is 40 ℃, so as to obtain the coke-inhibiting and increasing agent J.
Example 11
Example 11 differs from example 1 in that in example 11 the alkylphenol ethoxylate is n-pentane phenol ethoxylate and the sulfonate is a mixture of sodium hexadecyl phenyl sulfonate and sodium polyoxyethylene ether sulfonate to obtain the coke inhibiting and increasing agent K.
Example 12
Example 12 differs from example 1 in that in example 12 the alkylphenol ethoxylate is n-triacontylphenol ethoxylate, the sulfonate is a mixture of sodium n-hexane-yl-phenylsulfonate and sodium polyoxyethylene ether sulfonate, and the coke inhibition and income increasing agent L is obtained.
Comparative example 1
Comparative example 1 differs from example 1 in that 20 parts of lauryl ether phosphate, 40 parts of three-wire reduced oil, 30 parts of nonylphenol polyoxyethylene ether, 20 parts of a mixture of sodium dodecyl phenyl sulfonate and sodium polyoxyethylene ether sulfonate, and 10 parts of phenol are taken in comparative example 1 to obtain a scorch inhibiting and income increasing agent M.
Comparative example 2
Comparative example 2 differs from example 1 in that 60 parts of lauryl ether phosphate, 30 parts of three-wire reduced oil, 25 parts of nonylphenol polyoxyethylene ether and 5 parts of phenol are taken in comparative example 2 to obtain a scorch retarder N.
Comparative example 3
Comparative example 3 differs from example 1 in that 65 parts of lauryl ether phosphate, 35 parts of three-wire reduced oil and 20 parts of nonylphenol polyoxyethylene ether are taken in comparative example 3 to obtain a coke inhibition and yield increase agent O.
Comparative example 4
Comparative example 4 differs from example 1 in that 30 parts of a three-wire reduced oil, 50 parts of nonylphenol polyoxyethylene ether, 30 parts of a mixture of sodium dodecylphenylsulfonate and sodium polyoxyethylene ether sulfonate, and 10 parts of phenol were taken in comparative example 4 to obtain a scorch retarder P.
The coke inhibition and income increasing agents M-P are respectively taken, the coke inhibition and income increasing agents are weighed according to the adding ratio of the coke inhibition and income increasing agents to residual oil of 100 mug/g and are added into a delayed coking experiment device, the reaction temperature of a coking experiment is 500 ℃ and the reaction time is 2 hours, and the experiment data are used for verification, and the experiment results are shown in table 1 (blank experiments in which no coke inhibition and income increasing agents are added).
TABLE 1
| Coke inhibiting and income increasing agent | Light oil yield/% | Wax oil yield/% | Coke yield/% |
| Blank test | 42.77 | 12.98 | 25.19 |
| A | 53.46 | 17.34 | 20.64 |
| B | 53.51 | 17.39 | 20.58 |
| C | 53.49 | 17.37 | 20.60 |
| D | 53.48 | 17.36 | 20.61 |
| E | 53.50 | 17.38 | 20.60 |
| F | 53.49 | 17.36 | 20.62 |
| G | 52.80 | 17.09 | 20.84 |
| H | 53.41 | 17.32 | 20.88 |
| I | 53.49 | 17.37 | 20.60 |
| J | 52.91 | 17.18 | 20.98 |
| K | 53.44 | 17.35 | 20.63 |
| L | 53.45 | 17.32 | 20.65 |
| M | 45.71 | 13.96 | 23.19 |
| N | 42.73 | 13.95 | 25.15 |
| O | 43.74 | 12.93 | 26.18 |
| P | 42.75 | 12.97 | 25.16 |
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
the application adopts polyoxyethylene ether phosphate as an activation main body, wherein polyoxyethylene ether bonds have the characteristics of good stability to acid, alkali and salt, high temperature resistance and capability of being used in a larger temperature range. The polyoxyethylene ether phosphate is a commonly used surfactant, has the characteristics of anions and non-ions, has good intersolubility and compatibility with other surfactants, and can be well compatible with alkylphenol polyoxyethylene ether non-ionic surfactants and sulfonate anionic surfactants so as to cooperate with the alkylphenol polyoxyethylene ether nonionic surfactants to achieve the synergistic effect of the surfactants, so that the finally formed compound surfactant has stronger wettability, adsorptivity, permeability, dispersibility, emulsifying property, compatibilization and washing effect, further improves the dissolving capacity of an integral dispersion system in residual oil, and releases low-molecular hydrocarbons adsorbed by supramolecular structure cores in the residual oil raw materials to carry out thermal cracking reaction, thereby improving the yield of light oil.
Meanwhile, the active main polyoxyethylene ether phosphate and alkylphenol polyoxyethylene ether are surfactants with active hydrogen atoms; the phenol can prevent the influence of bad substances such as oxygen and the like, helps to capture and neutralize free radicals, and can lead aromatic hydrocarbon and olefin to be difficult to polymerize into coke at high temperature by using the high-temperature chain initiation terminator, so that the free radical reaction is stopped, namely the polycondensation reaction is relatively stopped. Both the functions are beneficial to reducing the free radical condensation reaction and polymerization reaction in the residual oil raw material, thereby inhibiting the generation of macromolecular compounds, further inhibiting the formation of colloid and asphaltene by dehydrogenation condensation and reducing the probability of final condensation into coke.
The coke inhibition and yield increase agent has excellent coking inhibition effect, and polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether, sulfonate and phenol are mainly surfactants, so that the coke inhibition and yield increase agent has a simple formula and wide raw material sources, and the components have good synergistic effect, so that the use of the surfactants is reduced, and the preparation cost of the coke inhibition and yield increase agent is further reduced.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The coke inhibition and income increasing agent is characterized by comprising, by weight, 35-65 parts of polyoxyethylene ether phosphate, 15-25 parts of alkylphenol polyoxyethylene, 10-20 parts of sulfonate, 5-10 parts of phenol and 15-35 parts of aromatic concentrated oil;
the polyoxyethylene ether phosphate is fatty acid polyoxyethylene ether phosphate and C 12 ~C 16 One or two of fatty alcohol polyoxyethylene ether phosphate esters;
the alkylphenol polyoxyethylene is C 5 ~C 30 Linear alkylphenol ethoxylates of (a);
the sulfonate is C 12 ~C 20 Alkyl aryl sulfonates of (2)And polyoxyethylene ether sulfonate;
the C is 12 ~C 20 The weight ratio of the alkylaryl sulfonate to the polyoxyethylene ether sulfonate is 2:3-6.
2. The coke-inhibiting and increasing agent according to claim 1, wherein the aromatic hydrocarbon concentrate is one or a mixture of two of a reduced-four-wire extract and a reduced-four-wire extract.
3. A method of preparing the coke inhibition and stimulation agent of any of claims 1 or 2, comprising:
step S1, stirring and mixing polyoxyethylene ether phosphate and aromatic concentrated oil for the first time to obtain a first mixed system;
and S2, stirring and mixing the first mixed system with alkylphenol ethoxylates, sulfonate and phenol for the second time to obtain the coke inhibition and income increasing agent.
4. The method according to claim 3, wherein the time for the first stirring and mixing and the time for the second stirring and mixing are each independently 1 to 2.5 hours.
5. The method according to claim 3, wherein the temperature of the first stirring and mixing and the temperature of the second stirring and mixing are respectively 50-70 ℃.
6. The method according to claim 3, wherein the stirring speeds of the first stirring and mixing and the second stirring are 500 to 1500r/min, respectively.
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