CN111925825A - Scale inhibition and dispersion agent and preparation method and application thereof - Google Patents
Scale inhibition and dispersion agent and preparation method and application thereof Download PDFInfo
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- CN111925825A CN111925825A CN202010739517.8A CN202010739517A CN111925825A CN 111925825 A CN111925825 A CN 111925825A CN 202010739517 A CN202010739517 A CN 202010739517A CN 111925825 A CN111925825 A CN 111925825A
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- 239000006185 dispersion Substances 0.000 title claims abstract description 25
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 56
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 43
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- 150000003254 radicals Chemical class 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000004140 cleaning Methods 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 24
- 239000006078 metal deactivator Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 34
- 230000002401 inhibitory effect Effects 0.000 claims description 21
- 229940126062 Compound A Drugs 0.000 claims description 14
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 14
- 229960002317 succinimide Drugs 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004939 coking Methods 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- -1 styryl octyl diphenylamine Chemical compound 0.000 claims description 6
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 5
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 5
- 229920002367 Polyisobutene Polymers 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 5
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 5
- 229910000071 diazene Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims description 4
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 claims description 2
- ZKWJQNCOTNUNMF-QXMHVHEDSA-N 2-[dimethyl-[3-[[(z)-octadec-9-enoyl]amino]propyl]azaniumyl]acetate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O ZKWJQNCOTNUNMF-QXMHVHEDSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- RVKKRRXSXPNVLU-UHFFFAOYSA-N C(CCCCCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCCCCC Chemical compound C(CCCCCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCCCCC RVKKRRXSXPNVLU-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 239000002455 scale inhibitor Substances 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 2
- 239000012459 cleaning agent Substances 0.000 claims 1
- 239000000852 hydrogen donor Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000945 filler Substances 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 239000000571 coke Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- PSAYJRPASWETSH-UHFFFAOYSA-N pyridine-2-carbonyl chloride Chemical compound ClC(=O)C1=CC=CC=N1 PSAYJRPASWETSH-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BFVOBXSKECUHSW-UHFFFAOYSA-N 4-n,4-n-di(butan-2-yl)benzene-1,4-diamine Chemical compound CCC(C)N(C(C)CC)C1=CC=C(N)C=C1 BFVOBXSKECUHSW-UHFFFAOYSA-N 0.000 description 1
- XLBVSXPCAYBWED-UHFFFAOYSA-N CC(C=C1)=C(CCC(NN)=O)C2=C1NN=N2 Chemical compound CC(C=C1)=C(CCC(NN)=O)C2=C1NN=N2 XLBVSXPCAYBWED-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZCLGVXACCAZJOX-UHFFFAOYSA-N ethyl 3-chloropropanoate Chemical compound CCOC(=O)CCCl ZCLGVXACCAZJOX-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical group CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- DXGIRFAFSFKYCF-UHFFFAOYSA-N propanehydrazide Chemical compound CCC(=O)NN DXGIRFAFSFKYCF-UHFFFAOYSA-N 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
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
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- 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)
- Detergent Compositions (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
The invention discloses a scale inhibition and dispersion agent. The scale inhibition and dispersion agent comprises the following components in percentage by mass: 20-30 wt% of cleaning dispersant, 0.5-5 wt% of metal deactivator, 0.5-10 wt% of antioxidant, 0.5-10 wt% of corrosion inhibitor, 0.1-1 wt% of free radical terminator, 0.1-1 wt% of diverter and the balance of solvent. Through the mutual matching of the components, the caking of the dirt can be effectively inhibited to form large dirt, and the large dirt is prevented from being aggregated and deposited in equipment; meanwhile, the existing large scale can be dissolved and dispersed into movable particles, so that the scale is conveniently discharged from equipment, devices and pipelines; meanwhile, the device has the effect of slowing down the corrosion of the equipment, and can effectively prolong the service life of the equipment and the device. Under the same process conditions, the problems of whole-tower pressure drop increase, difficult control of the dry point of the initial top product and the like caused by the reduction of the separation efficiency of the tray due to the scaling of the tray are alleviated or even eliminated.
Description
Technical Field
The invention belongs to the field of petrochemical additives, and particularly relates to a scale inhibition and dispersion agent, and a preparation method and application thereof.
Background
In the prior art, as the properties of raw oil become heavier, processing conditions of a processing device become more and more severe due to corrosion and the like, the problems of tower plate coking, oil slurry system scaling and the like of a refinery device occur, the problems of whole-tower pressure drop increase, difficulty in controlling the dry point of an initial top product and the like caused by the reduction of the separation efficiency of a tower tray, and a series of problems of frequent cleaning of a heat exchanger, increase of oil slurry circulation, reduction of steam yield and the like. Especially for packing coking, because the reduced pressure regular packing has small gaps, the coking is easy and the cleaning is difficult; after coke in the packing is formed, the coking rate will be faster the further the later, and the more dense the coke mass will be, the less easily it will be dispersed. The problem of coking of the pressure reducing filler is difficult to thoroughly solve in the current online running state, and the normal running of the device is greatly influenced.
Analysis of the tray fouling samples may result in tray fouling due to (1) ammonium salt deposition, (2) corrosion scale, (3) its entrained colloids/asphaltenes and some fine solid impurities.
However, the scale inhibitor in the current market has single component function and weak general applicability, so that the problem of inconsistent effect occurs in the using process.
Disclosure of Invention
The invention provides a scale inhibition and dispersion agent, which comprises the following components in percentage by mass: 20-30 wt% of cleaning dispersant, 0.5-5 wt% of metal deactivator, 0.5-10 wt% of antioxidant, 0.5-10 wt% of corrosion inhibitor, 0.1-1 wt% of free radical terminator, 0.1-1 wt% of diverter and the balance of solvent.
According to an embodiment of the present invention, the cleaning dispersant is at least one of polyisobutylene diimine, mono-pendant succinimide, and di-pendant succinimide.
According to an embodiment of the invention, the content of the cleaning dispersant is 23 to 28 wt%, illustratively 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%.
According to the embodiment of the invention, the metal passivator is at least one of benzotriazole, aminotriazole and thiadiazole.
According to an embodiment of the invention, the metal deactivator is present in an amount of 1 to 4 wt%, illustratively 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%.
According to an embodiment of the present invention, the antioxidant is selected from at least one of a hydrogen-donating antioxidant and an amine-type antioxidant. For example, the hydrogen-donating antioxidant is selected from high-temperature-resistant hydrogen-donating antioxidants, preferably benzyl alcohol, tetrahydronaphthalene, tetralone, decahydronaphthalene and the like. For example, the amine antioxidant is at least one of 4, 4-diisooctyldiphenylamine, N-di-sec-butyl-p-phenylenediamine, styryl-octyldiphenylamine, and didodecyldiphenylamine.
Preferably, the antioxidant comprises a hydrogen-donating antioxidant and an amine antioxidant in a mass ratio of 1 (0.5-5), and preferably comprises a hydrogen-donating antioxidant and an amine antioxidant in a mass ratio of 1 (1-3).
According to an embodiment of the invention, the antioxidant is present in an amount of 2 to 8 wt%, illustratively 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%.
According to an embodiment of the invention, the corrosion inhibitor is present in an amount of 2-8 wt%, illustratively 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%.
According to an embodiment of the present invention, the corrosion inhibitor comprises a compound a and a compound B, the compound a having a structure represented by formula (1):
the compound B is a compound with a structure shown in a formula (2):
wherein R is1、R3Are identical or different and are selected independently of one anotherH、C1-20An alkyl group; r4、R6Same or different, independently from each other selected from H, C1-20Alkyl radical, C2-20An alkenyl group; r2、R5Identical or different, independently of one another, from C1-20An alkylene group;
n is an integer of 1 or more.
According to an embodiment of the invention, R1、R3Same or different, independently from each other selected from H, C1-6An alkyl group; preferably, R1、R3And are each independently selected from H, methyl, ethyl, propyl. Illustratively, R1Is methyl, R3Is H.
According to an embodiment of the invention, R4、R6Identical or different, independently of one another, from C10-20Alkyl radical, C10-20An alkenyl group; preferably, R4、R6Same, selected from-C11H23、-C13H28or-C17H33。
According to an embodiment of the invention, R2、R5Identical or different, independently of one another, from C1-10An alkylene group; preferably, R2、R5Are identical and are independently selected from C1-4Alkylene groups such as methylene, ethylene.
According to an embodiment of the invention, n is selected from an integer from 1 to 10, for example n ═ 2, 3 or 4.
According to a preferred embodiment of the present invention, said compound a has the structure as shown in formula (1'):
wherein R is1、R2、R3Have the meaning as indicated above.
More preferably, the compound a has a structure as shown in formula (1 "):
according to a preferred embodiment of the invention, said compound B has the structure shown in formula (2'):
wherein R is4、R6Have the meaning as indicated above.
More preferably, the compound B has a structure as shown in any one of formulas (3) to (5):
according to an embodiment of the invention, the molar ratio of compound a and compound B in the corrosion inhibitor is (2-5: 1, illustratively 2:1, 3:1, 3.5:1, 4:1 or 5: 1.
According to an embodiment of the invention, the corrosion inhibitor contains compound A and compound B in a molar ratio of (2-5):1,
wherein the compound A has a structure shown in a formula (1 '), and the compound B has a structure shown in a formula (2');
preferably, the compound A has a structure shown in a formula (1'), and the compound B has a structure shown in any one of formulas (3) to (5).
According to an embodiment of the present invention, the compound a and the compound B may be prepared by a method known in the art.
According to an embodiment of the invention, the corrosion inhibitor has thermal stability. For example, the corrosion inhibitor is resistant to temperatures of 200 to 400 ℃, preferably 250 to 350 ℃.
According to an embodiment of the invention, the diverting agent comprises oleamidopropyl betaine and/or mesonic acid amidopropyl betaine.
According to an embodiment of the invention, the radical terminator comprises 2-sec-butyl-4-6-dinitrophenol and/or 4-tert-butylcatechol.
According to an embodiment of the invention, the content of the diverter and/or the radical terminator is 0.3-0.8 wt%, such as 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%.
According to an embodiment of the invention, the solvent is a miscella, e.g. 120#, 200#, 230# miscella.
The invention also provides a preparation method of the scale inhibition and dispersion agent, which comprises the following steps: uniformly mixing a cleaning dispersant, a free radical terminator, a diverter, an antioxidant and a solvent at 50-60 ℃ (such as 50 ℃, 52 ℃, 54 ℃, 55 ℃, 56 ℃, 58 ℃ and 60 ℃), sequentially adding a slow-release agent and a metal deactivator into the mixture, and uniformly mixing at 60-70 ℃ (such as 60 ℃, 62 ℃, 64 ℃, 65 ℃, 66 ℃, 68 ℃ and 70 ℃) to obtain the scale inhibition dispersant;
the cleaning dispersant, the free radical terminator, the diverter, the antioxidant, the slow release agent, the metal deactivator and the solvent have the mass ratio as described above.
The invention also provides application of the scale inhibition and dispersion agent in oil and gas field ground engineering. Preferably, the oil and gas field ground engineering comprises oil field pipelines, phase separators, fractionating towers, rectifying towers, pressure reducing towers, steam generators and the like; illustratively, the scale inhibiting and dispersing agent can be used for dissolving and dispersing coking on packing of each tower, scaling of a tower kettle of a fractionating tower and the like.
According to an embodiment of the invention, the scale inhibiting and dispersing agent is added in an amount of 10 to 200ppm, for example 20 to 160ppm, in each apparatus, device or pipeline.
According to an embodiment of the invention, the scale inhibiting and dispersing agent can be injected in stages, for example, the injection amount in the first stage is not more than 50ppm, and then the injection amount is increased by 10-20ppm stage by stage.
Definition and description of terms
Unless otherwise indicated, the definitions of groups and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. The definitions of the groups and the structures of the compounds in such combinations and after the combination are within the scope of the present specification.
“C1-C20"means having 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. "C2-C20"means having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. "C1-C10"means having 1,2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. "C10-C20"means having 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. For the same reason, "C1-C6"denotes a corresponding number of carbon atoms.
Alkyl groups: straight-chain or branched alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl.
Alkylene group: it has one less H atom than the linear or branched alkyl group, such as methylene, ethylene.
Alkenyl: straight-chain or branched alkenes, for example ethenyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkenyl also includes polyenes such as 1, 2-allenyl and 2, 4-hexadienyl.
The invention has the beneficial effects that:
the scale inhibition and dispersion agent provided by the invention can effectively inhibit the scale from caking to form large scale through the mutual matching of the components, and prevent the large scale from aggregating and depositing in equipment; meanwhile, the existing large scale can be dissolved and dispersed into movable particles, so that the scale is conveniently discharged from equipment, devices and pipelines; meanwhile, the device has the effect of slowing down the corrosion of the equipment, and can effectively prolong the service life of the equipment and the device.
The compounding of the components of the scale inhibition and dispersion agent reduces the scaling in equipment or pipelines, inhibits the coking rate, has strong adaptability and stable scale inhibition performance. Under the same process conditions, the problems of whole-tower pressure drop increase, difficult control of the dry point of the initial top product and the like caused by the reduction of the separation efficiency of the tray due to the scaling of the tray are alleviated or even eliminated.
Drawings
FIG. 1 is a graph showing the dissolution and dispersion of a coke scale sample in test example 1.
FIG. 2 is the change of gasification load and pressure drop of the vacuum tower before and after adding the scale inhibiting dispersant in test example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The following examples and comparative examples the preparation of compound a of formula (1 ") is carried out:
(a) reacting 3-ethyl chloropropionate with methylbenzotriazole to generate intermediate by using potassium carbonate as a reaction catalyst and acetone as a reaction solvent
Wherein the molar ratio of the potassium carbonate, the ethyl 3-chloropropionate to the methylbenzotriazole is 1:1:1, the reaction temperature is 90 ℃, and the reaction time is 3 hours.
(b) Using ethanol as a reaction solvent, and reacting the reaction product of the first step with hydrazine hydrate to generate the methylbenzotriazolepropanehydrazide
Wherein the molar ratio of the intermediate to the hydrazine hydrate is 1:1, the reaction temperature is 100 ℃, and the reaction time is 3 h.
(c) The method comprises the steps of taking ethyl acetate as a reaction solvent, and reacting potassium thiocyanate, 2-pyridine carbonyl chloride and methylbenzotriazole propionyl hydrazine to generate a compound A with a structure shown in a formula (1'), wherein the molar ratio of the potassium thiocyanate to the 2-pyridine carbonyl chloride to the methylbenzotriazole propionyl hydrazide is 1:1:0.8, the reaction temperature is 130 ℃, and the reaction time is 2 hours.
The preparation process of the scale inhibiting and dispersing agent in the following examples and comparative examples is as follows: uniformly mixing the cleaning dispersant, the free radical terminator, the diverter, the antioxidant and the solvent at 55 ℃, sequentially adding the slow release agent and the metal deactivator into the mixture, and uniformly mixing at 65 ℃ to obtain the scale inhibition dispersant; the amounts of the components are specified in the examples and comparative examples.
Example 1
The scale inhibition and dispersion agent comprises the following components in percentage by mass: 24 wt% of cleaning dispersant, 2 wt% of metal deactivator, 3 wt% of antioxidant, 5 wt% of corrosion inhibitor, 0.5 wt% of free radical terminator, 0.3 wt% of diverter and the balance of solvent;
the cleaning dispersant is single-hanging succinimide and double-hanging succinimide in a mass ratio of 1: 1;
the metal passivator is benzotriazole;
the antioxidant is decahydronaphthalene and N, N-di-sec-butyl-p-phenylenediamine in a mass ratio of 1: 3;
the corrosion inhibitor is obtained by uniformly mixing a compound A with a structure shown in a formula (1') and a compound B with a structure shown in a formula (3) according to a molar ratio of 2.5: 1.
The free radical terminator is 2-sec-butyl-4-6-dinitrophenol;
the diverting agent is oleamide propyl betaine;
the solvent is No. 120 solvent oil.
Example 2
The scale inhibition and dispersion agent comprises the following components in percentage by mass: 28 wt% of cleaning dispersant, 4 wt% of metal deactivator, 6 wt% of antioxidant, 7 wt% of corrosion inhibitor, 0.7 wt% of free radical terminator, 0.6 wt% of diverter and the balance of solvent;
the cleaning dispersant is polyisobutylene diimine, single-hanging succinimide and double-hanging succinimide in a mass ratio of 2:1: 1;
the metal passivator is aminotriazole;
the antioxidant is benzyl alcohol and styryl octyl diphenylamine in a mass ratio of 1: 1;
the corrosion inhibitor is obtained by uniformly mixing a compound A with a structure shown in a formula (1') and a compound B with a structure shown in a formula (4) according to a molar ratio of 3: 1.
The free radical terminator is 4-tert-butyl catechol;
the diverting agent is mesonic acid amide propyl betaine;
the solvent is 200# solvent oil.
Example 3
The scale inhibition and dispersion agent comprises the following components in percentage by mass: 20 wt% of cleaning dispersant, 5 wt% of metal passivator, 1 wt% of antioxidant, 10 wt% of corrosion inhibitor, 0.8 wt% of free radical terminator, 1 wt% of diverter and the balance of solvent;
the cleaning dispersant is polyisobutylene diimine, single-hanging succinimide and double-hanging succinimide in a mass ratio of 1:1: 1;
the metal passivator is amino triazole and thiadiazole in a mass ratio of 2: 3;
the antioxidant is benzyl alcohol and styryl octyl diphenylamine in a mass ratio of 1: 1;
the corrosion inhibitor is prepared by uniformly mixing a compound A with a structure shown in a formula (1') and a compound B with a structure shown in a formula (5) according to a molar ratio of 4: 1.
The free radical terminator is 4-tert-butyl catechol;
the diverting agent is mesonic acid amide propyl betaine;
the solvent is 200# solvent oil.
Example 4
The scale inhibition and dispersion agent comprises the following components in percentage by mass: 30 wt% of cleaning dispersant, 2 wt% of metal deactivator, 8 wt% of antioxidant, 8 wt% of corrosion inhibitor, 1 wt% of free radical terminator, 1 wt% of diverter and the balance of solvent;
the cleaning dispersant is polyisobutylene diimine, single-hanging succinimide and double-hanging succinimide in a mass ratio of 1:1: 1;
the metal passivator is amino triazole and thiadiazole in a mass ratio of 2: 3;
the antioxidant is benzyl alcohol and styryl octyl diphenylamine in a mass ratio of 1: 1;
the corrosion inhibitor is obtained by uniformly mixing a compound A with a structure shown in a formula (1') and a compound B with a structure shown in a formula (3) according to a molar ratio of 3.5: 1.
The free radical terminator is 4-tert-butyl catechol;
the diverting agent is mesonic acid amide propyl betaine;
the solvent is 200# solvent oil.
Comparative example 1
The scale inhibiting and dispersing agent of the comparative example is different from the content of the following components in example 1: 15 wt% of cleaning dispersant, 0.1 wt% of antioxidant, 1.5 wt% of free radical terminator and 1.5 wt% of diverter. The rest is the same as in example 1.
Comparative example 2
The scale inhibiting and dispersing agent of the comparative example is different from the content of the following components in example 1: 35 wt% of cleaning dispersant, 12 wt% of slow release agent, 12 wt% of antioxidant, 1.5 wt% of free radical terminator and 0.05 wt% of diverter. The rest is the same as in example 1.
Comparative example 3
The scale inhibiting and dispersing agent of the comparative example is different from the content of the following components in example 1: 0.2 wt% of antioxidant, 1.3 wt% of free radical terminator, 1.5 wt% of diverter and 0.2 wt% of metal passivator, and does not contain corrosion inhibitor. The rest is the same as in example 1.
Test example 1 dissolution and dispersion test of coke
The coke with coked filler is taken from a decompression tower as a scale sample, 5g of the coke scale sample is weighed and respectively placed in the 120# solvent oil, the scale inhibition dispersant solutions provided in the examples 1-4 and the comparative examples 1-3 (the scale inhibition dispersant solutions are prepared by diluting the 120# solvent oil by 100 times), the mixture is heated at the constant temperature of 80 ℃, and the dispersion condition of the scale sample in each system is observed after 2 hours.
As shown in the dispersion situation of FIG. 1, it can be seen that the pure solvent oil has no dispersion effect on the scale sample (sample D0 in FIG. 1), the scale inhibiting and dispersing agent provided in examples 1-4 can completely dissolve and disperse the scale sample (samples in examples 1-4 correspond to samples S1-S4 in FIG. 1 respectively), and the scale inhibiting and dispersing agent provided in comparative examples 1-3 has significantly weaker dissolution and dispersion effect on the scale sample (samples in comparative examples 1-3 correspond to samples D1-D3 in FIG. 1 respectively) than the samples in examples.
Test example 2 effect of the dispersant of example 1 on a pressure reducing column
The scale inhibition and dispersion agent of the example 1 is tried in 27 days 6 and 27 days 2019 and 8 and 28 days 2019 by four times of distillation, the dispersion agent is added into a high-temperature corrosion inhibitor tank of the device, and the high-temperature corrosion inhibitor injection flow is adopted, and a metering pump is used for 7m3The injection amount of 50ppm dispersant in/h feeding amount is injected into the inlet of a five-reducing pump P1043/1.2 through an injection pipeline, enters a decompression washing oil line and a three-reducing middle return line through the five-reducing pump, and then enters a decompression tower along with washing oil and the three-reducing middle return line.
The gasification load and the total column pressure drop of the vacuum column before and after the addition of the scale inhibiting dispersant of example 1 with time are shown in FIG. 2. As can be seen from the view of figure 2,
1) after the dispersing agent is injected from the bottom of 6 months to the bottom of 7 months, the pressure drop is in a descending trend along with the reduction of the pressure reduction load, and the pressure drop is slightly increased from the opening degree of two curves of the pressure drop and the load to the bottom of July, so that the pressure drop of the injection agent in 7 months does not rise and has a better trend qualitatively.
2) In late 8 months to late 8 months (about 16 days), the pressure drop increased with the increase in the decompression load, but slightly increased from the maximum pressure drop at the end of 6 months at the initial injection. The reason is that the dispersant enters the filler from the upper part of the filler along with the reflux, the load of 7 months is always in a descending trend after the agent is injected from the bottom of 6 months, under the action of the dispersant of nearly one month, the coking dirt on the upper layer of the filler is dissolved and dispersed along with the dispersant, and the fine coke powder is gradually settled towards the lower part of the filler along with the reflux flushing oil. When the load of the decompression gas phase gradually rises, the rising gas phase amount and pressure at the lower part of the filler gradually increase, and the small granular coke powder dissolved and dispersed by the dispersing agent is difficult to fall off freely from the bottom of the filler, so that more small granular coke powder is gathered at the lower part of the filler, and the decompression pressure drop inevitably further rises along with the rising of the load, which is a natural process according with the dissolving and dispersing of the coke scale of the filler by the dispersing agent.
3) From the middle ten days of 8 months, the pressure reducing load suddenly decreases, the pressure reducing pressure drop is greatly reduced, and the pressure reducing load rises along with the pressure drop when the second wave rises from the 20 th day of 8 months to the 8 th month end. However, when the pressure drop during the load increase in late 8 months is compared with the pressure drop in the previous same load state, the pressure drop during the load increase in late 8 months is slightly lower than the pressure drop in the previous same load state. The change in pressure drop can be illustrated by comparing the intersection of two black vertical lines with two horizontal lines in fig. 2 under the same load.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The scale inhibition and dispersion agent is characterized by comprising the following components in percentage by mass: 20-30 wt% of cleaning dispersant, 0.5-5 wt% of metal deactivator, 0.5-10 wt% of antioxidant, 0.5-10 wt% of corrosion inhibitor, 0.1-1 wt% of free radical terminator, 0.1-1 wt% of diverter and the balance of solvent.
2. The scale inhibiting and dispersing agent of claim 1, wherein the cleaning and dispersing agent is at least one of polyisobutylene diimine, mono-and di-succinimide.
Preferably, the cleaning dispersant is present in an amount of 23 to 28 wt%, illustratively 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%.
3. The scale inhibiting and dispersing agent of claim 1 or 2, wherein the metal deactivator is at least one of benzotriazole, aminotriazole and thiadiazole.
Preferably, the metal deactivator is present in an amount of 1 to 4 wt%, illustratively 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%.
4. The scale inhibiting and dispersing agent according to any one of claims 1 to 3, wherein the antioxidant is at least one selected from a hydrogen donor antioxidant and an amine antioxidant. Preferably, the hydrogen-supplying antioxidant is selected from high-temperature-resistant hydrogen-supplying antioxidants, preferably benzyl alcohol, tetrahydronaphthalene, tetralone, decahydronaphthalene and the like. Preferably, the amine antioxidant is at least one of 4, 4-diisooctyl diphenylamine, N-di-sec-butyl p-phenylenediamine, styryl octyl diphenylamine and didodecyl diphenylamine.
Preferably, the antioxidant comprises a hydrogen-donating antioxidant and an amine antioxidant in a mass ratio of 1 (0.5-5), and preferably comprises a hydrogen-donating antioxidant and an amine antioxidant in a mass ratio of 1 (1-3).
Preferably, the antioxidant is present in an amount of 2 to 8 wt%, illustratively 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%.
5. The dispersion and scale inhibitor according to any of claims 1-4, wherein the corrosion inhibitor is present in an amount of 2-8 wt%, illustratively 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%.
Preferably, the corrosion inhibitor contains a compound A and a compound B, wherein the compound A has a structure shown in a formula (1):
the compound B is a compound with a structure shown in a formula (2):
wherein R is1、R3Same or different, independently from each other selected from H, C1-20An alkyl group; r4、R6Same or different, independently from each other selected from H, C1-20Alkyl radical, C2-20An alkenyl group; r2、R5Identical or different, independently of one another, from C1-20An alkylene group;
n is an integer of 1 or more.
Preferably, R1、R3Same or different, independently from each other selected from H, C1-6An alkyl group; preferably, R1、R3And are each independently selected from H, methyl, ethyl, propyl. Illustratively, R1Is methyl, R3Is H.
Preferably, R4、R6Identical or different, independently of one another, from C10-20Alkyl radical, C10-20An alkenyl group; preferably, R4、R6Same, selected from-C11H23、-C13H28or-C17H33。
Preferably, R2、R5Identical or different, independently of one another, from C1-10An alkylene group; preferably, R2、R5Are identical and are independently selected from C1-4Alkylene groups such as methylene, ethylene.
Preferably, n is selected from an integer from 1 to 10, for example n ═ 2, 3 or 4.
6. The scale inhibiting and dispersing agent of claim 5, wherein the compound A has a structure shown in formula (1'):
wherein R is1、R2、R3Have the meaning as indicated above.
More preferably, the compound a has a structure as shown in formula (1 "):
preferably, the compound B has a structure as shown in formula (2'):
wherein R is4、R6Have the meaning as indicated above.
More preferably, the compound B has a structure as shown in any one of formulas (3) to (5):
preferably, the molar ratio of compound a and compound B in the corrosion inhibitor is (2-5):1, illustratively 2:1, 3:1, 3.5:1, 4:1 or 5: 1.
Preferably, the corrosion inhibitor contains a compound A and a compound B in a molar ratio of (2-5):1,
wherein the compound A has a structure shown in a formula (1 '), and the compound B has a structure shown in a formula (2');
preferably, the compound A has a structure shown in a formula (1'), and the compound B has a structure shown in any one of formulas (3) to (5).
7. The scale inhibiting and dispersing agent of any one of claims 1 to 6, wherein the diverter comprises oleamidopropyl betaine and/or mesonic acid amidopropyl betaine.
Preferably, the radical terminator comprises 2-sec-butyl-4-6-dinitrophenol and/or 4-tert-butylcatechol.
Preferably, the diverter and/or the radical terminator is present in an amount of 0.3 to 0.8 wt%, such as 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%.
8. The scale inhibiting and dispersing agent of any one of claims 1 to 7, wherein the solvent is a solvent oil, such as 120#, 200#, 230# solvent oil.
9. The preparation method of the scale inhibiting and dispersing agent of any one of claims 1 to 8, which is characterized by comprising the following steps: uniformly mixing a cleaning dispersant, a free radical terminator, a diverter, an antioxidant and a solvent at 50-60 ℃, sequentially adding a slow release agent and a metal deactivator into the mixture, and uniformly mixing at 60-70 ℃ to obtain the scale inhibition dispersant;
the cleaning dispersant, the free radical terminator, the diverter, the antioxidant, the slow release agent, the metal deactivator and the solvent have the mass ratio as set forth in any one of claims 1 to 8.
10. Use of the scale inhibiting and dispersing agent of any one of claims 1 to 8 in oil and gas field surface engineering. Preferably, the oil and gas field ground engineering comprises oil field pipelines, phase separators, fractionating towers, rectifying towers, pressure reducing towers, steam generators and the like; illustratively, the scale inhibition and dispersion agent is used for dissolving and dispersing coking on packing of each tower and scaling of a tower kettle of a fractionating tower.
Preferably, the filling amount of the scale inhibiting and dispersing agent in each device, equipment or pipeline is 10-200ppm, such as 20-160 ppm.
Preferably, the scale inhibiting and dispersing agent is injected in stages, for example, the injection amount in the first stage is not more than 50ppm, and then is increased by 10-20ppm stage by stage.
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