CN1013578B - Preparation method of corrosion and scale inhibitor of thiophosphate ester and phosphate ester imidazoline derivatives - Google Patents
Preparation method of corrosion and scale inhibitor of thiophosphate ester and phosphate ester imidazoline derivativesInfo
- Publication number
- CN1013578B CN1013578B CN 87104560 CN87104560A CN1013578B CN 1013578 B CN1013578 B CN 1013578B CN 87104560 CN87104560 CN 87104560 CN 87104560 A CN87104560 A CN 87104560A CN 1013578 B CN1013578 B CN 1013578B
- Authority
- CN
- China
- Prior art keywords
- water soluble
- preparation
- corrosion
- soluble mixt
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 13
- 230000007797 corrosion Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 12
- -1 thiophosphate ester Chemical class 0.000 title claims description 9
- 239000002455 scale inhibitor Substances 0.000 title abstract 2
- 229910019142 PO4 Inorganic materials 0.000 title 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 title 1
- 239000010452 phosphate Substances 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229920000768 polyamine Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002461 imidazolidines Chemical class 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 2
- 229930195729 fatty acid Natural products 0.000 abstract 2
- 239000000194 fatty acid Substances 0.000 abstract 2
- 150000004665 fatty acids Chemical class 0.000 abstract 2
- DZXSOSQSLWSODC-UHFFFAOYSA-N 4,5-dihydro-1h-imidazole;phosphoric acid Chemical class C1CN=CN1.OP(O)(O)=O DZXSOSQSLWSODC-UHFFFAOYSA-N 0.000 abstract 1
- 239000013043 chemical agent Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000000116 mitigating effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The corrosion and scale inhibitor synthesized by the method is a mixture containing fatty acid and resin acid or a compound of fatty acid and polyamine. The thiophosphate or phosphate imidazoline derivative is used in oil field sewage treatment and reinjection water system, and has obvious corrosion and scale inhibiting effect on steel pipeline and equipment without needing other chemical agent. The corrosion inhibition rate reaches about 80%. The scale inhibition rate reaches 80-100%.
Description
The present invention is the preparation method who is used for the thiophosphatephosphorothioate of disposing polluted water in oil and re-injection water system and imidazoline phosphate ester derivative corrosion inhibiting and descaling agent.
The present invention according to petroleum department's scientific information research correlation technique is not found in external nearly 10 years relevant Searches of Patent Literature as yet.
Adopt the material of synthetic method of the present invention preparation, be used for disposing polluted water in oil and re-injection water system to the corrosion that slows down steel equipment with prevent to have significant effect at the structures surface scale.
The preparation method of thiophosphatephosphorothioate of the present invention and imidazoline phosphate ester derivative utilizes the technology of preparing of existing tetrahydroglyoxaline to synthesize the compound of tetrahydroglyoxaline type, as example 1 and 2.This compounds is used as inhibiter, and is existing at home and abroad historical for many years, generally all is to adopt lipid acid and polyamines reaction to make.From application facet oil soluble and water-soluble two classes are arranged, the oil soluble tetrahydroglyoxaline is owing in aqueous phase dissolving, bad dispersibility, be difficult for using in water system.Mineral acid such as HCL and organic acid such as the CH of adopting when in water system, using more
3COOH etc. neutralize and make water miscible imidazoline salt, these salt compounds generally are used in acidic medium such as the treatment solutions such as pickling and oil well acidation pressure break, do not see the report that is useful on disposing polluted water in oil and re-injection water system, this compounds does not have the scale inhibition effect yet.
The imidazolidine derivatives that this preparation method makes has inhibition and scale effect.The preparation method of tetrahydroglyoxaline is except that taking lipid acid, the mixture such as the Yatall MA of lipid acid and resin acid have also been adopted, for obtaining water-soluble products, adopted the technological line of addition reaction to synthesize water miscible imidazolinium compounds, for the corrosion mitigating effect that improves this compound and make it have scale effect, again with above-mentioned substance and P
2S
5Or P
2O
5Deng the material effect, made water miscible sulfo-phosphide imidazolidine derivatives at last, its corrosion mitigating effect reaches about 80% in the oxygen-containing water system, and scale inhibition effect reaches 80～100%.With the explanation of preparation procedure example, wherein example 1, example 2 are that prior art, example 3～example 8 are invention technology below.
The preparation procedure example:
Example 1: 0,440 kilogram of (1 mole) Yatall MA and 0.1032 kilogram of (1 mole) polyamines adding are equipped with agitator, in the reaction flask of condenser and water trap.Add an amount of band aqua and bathe the temperature backflow at 150～190 ℃, the theoretical water generation reaction of deviating from more than 85% makes brown dope at last.
R1 is that the remaining base of lipid acid contains the C atomicity less than 17 in the formula, and R2 is that the remaining base of resinous acid contains the C atomicity less than 21.n=2～4 integers.
Example 2: 0.2825 kilogram of (1 mole) oleic acid and 0.1032 kilogram of (1 mole) polyamines adding are equipped with agitator, in the flask of condenser and water trap, add an amount of band aqua again and bathe temperature at 150 °～190 ℃ and reflux, deviate from the theoretical water generation reaction more than 85% and obtain a brown product.
R is that the remaining base of oleic acid contains C atomicity 16.n=2～4 integers in the formula.
Example 3: take by weighing example 1 product 0.2535 kilogram (0.5 mole) and proper catalyst and add in the pressure reaction still, be warmed up to 100～140 ℃ and add 0.110～0.440 kilogram of (2.5～10 moles) oxyethane again, constant temperature was 0.5 hour after reaction finished, and obtained a water miscible brown viscous mixture A and B.
P+q+p ' in the formula+q '=m
m＝2.5～10
Example 4: take by weighing example 2 products 0.1725 kilogram (0.5 mole) and proper catalyst and add in the reactor, be warmed up to 100～150 ℃ and add 0.110～0.330 kilogram of (2.5～7.5 moles) oxyethane again, reaction finishes, and makes a water-soluble brown thickness product D.
In the formula: p+q=m m=2.5～7.5
Example 5, take by weighing 0.0652 kilogram of (about 0.08 mole) example 3 product and 0.0178～0.0045 kilogram of (about 0.08～0.02 mole) P
2S
5, add in the reactor have agitator 10～50 ℃ of stirrings, be warmed up to 90～140 ℃ of constant temperature 2～7 hours, make a brown thickness, the homogeneous final product.
Example 6, take by weighing 0.057 kilogram of (about 0.1 mole) example 4 product and 0.0223～0.0045 kilogram of (0.1～0.02 mole) P
2S
5Adding has in the flask of agitator, then heats up in 90 ℃～150 ℃ reactions 1～6 hour 10～50 ℃ of stirrings, produces a brown thickness, the homogeneous phase final product.
Example 7, take by weighing 0.0815 kilogram of example 3 product (about 0.1 mole) and 0.0142～0.00284 kilogram of (0.1～0.02 mole) P
2O
5Add and have in the flask of agitator, after low temperature stirs, heat up in 90～140 ℃ of reactions after 1～5 hour, add average molecular weight again and be 217 alcohol mixture 0.0145 kilogram (about 0.067 mole), make brown homogeneous phase final product in 110 ℃～140 ℃ isothermal reactions 2～6 hours.
R3 is an alkyl in the formula, contains C atomicity 9～12.
Example 8: take by weighing 0.057 kilogram of example 4 product (about 0.1 mole) and 0.0142～0.00284 kilogram of (0.1～0.02 mole) P
2O
5Join in the flask that has agitator, low temperature stirs, and then is warmed up to 85～150 ℃, react 1～6 hour, adds average molecular weight again and be 0.0145 kilogram of 217 alcohol mixture, reacts 2～6 hours in 100～150 ℃, makes brown heavy-gravity homogeneous phase final product.
R in the formula
3Be alkyl
Corrosion mitigating effect: see Table 1
Test conditions: water quality, the Shengli Oil Field station oil-containing on-the-spot water of oxygen that exposes to the sun, test piece, 75 * 12 * 1.5mm plain carbon stool sheet static steel 12 days, 50 ℃ of test temperatures.
Scale inhibition effect: see Table 2
Assessment method: use the quantitative chemical analysis method.
Operation: with dosing water sample and blank not dosing of water water sample, the calcium ion [Ca that then measured in the constant temperature water sample in 5 hours at 70 ℃ of constant temperature with complexometry
++] content, obtain scale inhibition performance.
Table 2
Concentration
Medicine sample scale inhibition performance (%)
PPm
Example 5 products 10 62～63
20 79～92
Example 6 products 10 84～96
20 89～96
Example 7 products 10 65.2
20 78.3
Example 8 products 10 90.5～100
20 100
Claims (4)
1, a kind of preparation method of thiophosphatephosphorothioate imidazolidine derivatives corrosion inhibiting and descaling agent, it comprises that at first making Yatall MA and n wherein is the polyamine compounds NH of 2 to 3 integer
2(CH
2CH
2NH)
nH,
Make a kind of water soluble mixt with reacting ethylene oxide, this water soluble mixt reacted 2～7 hours at 90～140 ℃ with thiophosphoric anhydride more then.
2, a kind of preparation method of imidazoline phosphate ester derivative corrosion inhibiting and descaling agent, it comprises that at first making Yatall MA and n wherein is the polyamine compounds NH of 2 to 3 integer
2(CH
2CH
2NH)
nA kind of water soluble mixt that H and reacting ethylene oxide make, then this water soluble mixt again with Vanadium Pentoxide in FLAKES 90～140 ℃ the reaction 1～5 hour, and then with average molecular weight be 217 alcohol mixtures 110～140,20 ℃ the reaction 2～6 hours.
3, a kind of preparation method of thiophosphatephosphorothioate imidazolidine derivatives corrosion inhibiting and descaling agent, it comprises that at first making oleic acid and n wherein is the polyamine compounds NH of 2 to 3 integer
2(CH
2CH
2NH)
nA kind of water soluble mixt that H and reacting ethylene oxide make, this water soluble mixt reacted 1～6 hour at 90～150 ℃ with Vanadium Pentoxide in FLAKES more then.
4, a kind of preparation method of imidazoline phosphate ester derivative corrosion inhibiting and descaling agent, it comprises that at first making oleic acid and n wherein is the polyamine compounds NH of 2 to 3 integer
2(CH
2CH
2NH)
nA kind of water soluble mixt that H and reacting ethylene oxide make, then this water soluble mixt again with Vanadium Pentoxide in FLAKES 85～150 ℃ of reactions 1～6 hour, and then with average molecular weight be that 217 alcohol mixture was 100～150 ℃ of reactions 2～6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87104560 CN1013578B (en) | 1987-06-27 | 1987-06-27 | Preparation method of corrosion and scale inhibitor of thiophosphate ester and phosphate ester imidazoline derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87104560 CN1013578B (en) | 1987-06-27 | 1987-06-27 | Preparation method of corrosion and scale inhibitor of thiophosphate ester and phosphate ester imidazoline derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030263A CN1030263A (en) | 1989-01-11 |
| CN1013578B true CN1013578B (en) | 1991-08-21 |
Family
ID=4814926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87104560 Expired CN1013578B (en) | 1987-06-27 | 1987-06-27 | Preparation method of corrosion and scale inhibitor of thiophosphate ester and phosphate ester imidazoline derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013578B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038697C (en) * | 1995-04-19 | 1998-06-10 | 何秋霞 | Corrosion inhibitor for corrosion system of HCl-H2S-H2O |
| CN100400712C (en) * | 2003-05-08 | 2008-07-09 | 上海久安水质稳定剂厂 | Prepn of anticorrosive scale-inhibiting film |
| CN101230260B (en) * | 2007-11-01 | 2011-04-27 | 新疆德蓝股份有限公司 | Compound inhibitor for exploitation of oil-gas field and preparation method thereof |
| CN102650061B (en) * | 2012-05-07 | 2014-10-01 | 中国海洋石油总公司 | High-temperature corrosion inhibitor for restraining corrosion of high-acid value crude oil and application of high-temperature corrosion inhibitor |
| CN102965149B (en) * | 2012-12-11 | 2014-06-25 | 江苏汉光实业股份有限公司 | Preparation method of oil soluble corrosion inhibitor |
| CN103756660A (en) * | 2013-10-11 | 2014-04-30 | 中国石油天然气股份有限公司 | High-temperature-resistant corrosion inhibitor special for huff and puff of rocket power composite heat carrier |
| CN108192088B (en) * | 2017-12-29 | 2020-10-30 | 岳阳凯门水性助剂有限公司 | Anti-flash rust agent and preparation method and application thereof |
| CN108251087B (en) * | 2018-01-23 | 2020-10-13 | 中国石油天然气股份有限公司 | Carbon dioxide flooding injection well annulus protection fluid and preparation method and use method thereof |
| CN110127871B (en) * | 2019-05-21 | 2022-01-11 | 四川文理学院 | Novel scale inhibitor and application thereof |
| CN110028170B (en) * | 2019-05-21 | 2022-01-25 | 四川文理学院 | Efficient scale inhibitor and application thereof |
| CN110468419B (en) * | 2019-09-10 | 2021-03-30 | 艾茵化学(深圳)有限公司 | High-salt-resistance metal antirust agent and preparation method thereof |
-
1987
- 1987-06-27 CN CN 87104560 patent/CN1013578B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030263A (en) | 1989-01-11 |
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