CN105601668A - Preparation method of low-phosphorous corrosion and scale inhibitor PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid) - Google Patents
Preparation method of low-phosphorous corrosion and scale inhibitor PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid) Download PDFInfo
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- CN105601668A CN105601668A CN201510981542.6A CN201510981542A CN105601668A CN 105601668 A CN105601668 A CN 105601668A CN 201510981542 A CN201510981542 A CN 201510981542A CN 105601668 A CN105601668 A CN 105601668A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000007797 corrosion Effects 0.000 title claims abstract description 11
- 238000005260 corrosion Methods 0.000 title claims abstract description 11
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 7
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 title abstract 6
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 15
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims abstract description 13
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000498 cooling water Substances 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000003134 recirculating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- -1 alkane esters Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- ZNFNDZCXTPWRLQ-UHFFFAOYSA-N butane-1,1,1-tricarboxylic acid Chemical class CCCC(C(O)=O)(C(O)=O)C(O)=O ZNFNDZCXTPWRLQ-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of low-phosphorous corrosion and scale inhibitor PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid). Certain amounts of diethyl phosphite and diethyl maleate are added to a reaction kettle, a condensation reflux device and a stirrer are started, a certain amount of a catalyst A is slowly dropwise added under the stirring condition that the revolving speed of the stirrer is 200 r/min, and the mixture reacts for 1 h after the temperature is increased to 100 DEG C; then the temperature is decreased to 50 DEG C, a certain amount of ethyl acrylate is added, and the mixture reacts for 8 h in the stirred state; then a certain amount of a catalyst B is added to the reaction kettle, the mixture is heated to 80 DEG C for hydrolysis for 0.5 h, and a finally obtained product, namely, PBTCA, is a yellowish-brown viscous liquid. The preparation method of PBTCA has the advantages of simple process route, convenience in operation, low three-waste emission and the like, and can be widely applied to corrosion and scale inhibition of industrial recirculating cooling water systems.
Description
One, technical field
The invention belongs to environmental technology field, be specifically related to the preparation method of a kind of low-phosphorus corrosion and scale inhibitor PBTCA.
Two, background technology
PBTCA (2-phosphonate group-1,2,4 butane tricarboxylates) is the corrosion inhibiting and descaling agent that a kind of phosphorus content is very low, and in molecule, the content of phosphorus onlyAccount for 11.5% left and right of PBTCA gross mass, this is corrosion inhibiting and descaling agent HEDP (phosphorus content accounts for 30.1%) and ATMP than conventional phosphinePhosphorus content in (phosphorus content accounts for 31.1%) is much lower, and PBTCA possesses good scale-inhibiting properties and corrosion inhibition simultaneously.
The preparation method of PBTCA in " " organic chemistry ", 1965, the 30 12 phases of volume, 4020-4025 page " is with sub-phosphorusAcid three alkane esters, maleic acid monoesters and acrylonitrile are raw material, first tricresyl phosphite alkane ester are reacted and produce phosphonic acids fourth with maleic acid monoestersDiacid four alkane esters, it carries out Michael addition reaction with acrylonitrile again and makes five yuan of esters that PBTCA is corresponding, then this ester is existedUnder acid condition, hydrolysis makes PBTCA. This preparation method's process route complexity, not only can produce hypertoxic cyanogen in course of reactionCompound, and can cause secondary pollution to environment. The present invention is with diethyl phosphite, diethyl maleate and acrylic acidEthyl ester is raw material, under catalyst action, prepares PBTCA. The method reaction condition gentleness, production operation is easy to control, process flowJourney is simple, and three wastes discharge amount is few.
Three, summary of the invention
The object of the invention is taking diethyl phosphite, diethyl maleate and ethyl acrylate as raw material, at catalystThe lower preparation PBTCA of effect.
Cardinal principle of the present invention: reaction (1) is adding base catalyst A for diethyl phosphite and diethyl maleateCondition under there is nucleophilic addition and generate diethyl phosphonate base diethyl succinate; Reaction (2) is for generating in reaction (1)Product and ethyl acrylate generation nucleophilic addition, generate 2-diethyl phosphonate butane, one tricarboxylic acids ethyl ester; Anti-in (3)Ying Zhong, 2-diethyl phosphonate butane one tricarboxylic acids ethyl ester issues unboiled water solution in catalyst B effect, hydrolysate be PBTCA withThe mixture of ethanol.
The technical solution used in the present invention is: a certain amount of diethyl phosphite and diethyl maleate added in reactor,Open condensation reflux unit, under the stirring condition that is 200r/min at agitator speed, slowly drip a certain amount of catalyst A, treatAfter temperature rise to 100 DEG C, react 1 hour. Then be cooled to 50 DEG C, add a certain amount of ethyl acrylate, at stirringLower reaction 8h. In reactor, add a certain amount of catalyst B again, be warming up to 80 DEG C of heating hydrolysis 0.5h, finally obtainProduct is yellowish-brown thick liquid, is PBTCA of the present invention. Wherein diethyl phosphite, diethyl maleate, thirdOlefin(e) acid ethyl ester and catalyst A add mol ratio: 1:1:1:0.8. Catalyst A is the ethylenediamine of mass fraction 99%, urgesAgent B is the concentrated hydrochloric acid of mass fraction 37.5%.
This PBTCA preparation method of the present invention has the advantages such as process route is simple, easy and simple to handle, " three wastes " discharge is few,Can be widely used in the corrosion-mitigation scale-inhibition of industrial circulating cooling water system.
Four, brief description of the drawings
Fig. 1 is the infared spectrum of PBTCA of the present invention
Five, detailed description of the invention
The preparation method of a kind of low-phosphorus corrosion and scale inhibitor PBTCA provided by the invention is as follows:
A certain amount of diethyl phosphite and diethyl maleate are added in reactor, open condensation reflux unit, stirringMix under the stirring condition that device rotating speed is 200r/min and slowly to drip a certain amount of catalyst A, reaction after temperature rise to 100 DEG C1h. Then be cooled to 50 DEG C, add a certain amount of ethyl acrylate, under stirring, react 8h. In reactor, add againEnter a certain amount of catalyst B, be warming up to 80 DEG C of heating hydrolysis 0.5h, the product finally obtaining is yellowish-brown thick liquid, isPBTCA of the present invention. Wherein diethyl phosphite, diethyl maleate, ethyl acrylate and catalyst A are thrownAdding mol ratio is: 1:1:1:0.8. Catalyst A is the ethylenediamine of mass fraction 99%, and catalyst B is mass fraction 37.5%Concentrated hydrochloric acid.
The molecular weight of diethyl phosphite is 138, and the molecular weight of diethyl maleate is 172, and the molecular weight of ethylenediamine is60, the molecular weight of ethyl acrylate is that the molecular weight of 100, PBTCA is 270.
4 embodiment of the present invention are below provided
Embodiment 1
In reactor, add 6.9g diethyl phosphite and 8.6g maleic diethylester, open condensation reflux unit, stirringDevice rotating speed is 200r/min, slowly drips 2.4g catalyst A at agitator speed under the stirring condition that is 200r/min, treats temperatureAfter rising to 100 DEG C, degree reacts 1h. Then be cooled to 50 DEG C, add 5.0g ethyl acrylate, under stirring, react 8h.Toward the catalyst B that adds 8mL in reactor, be warming up to 80 DEG C of heating hydrolysis 0.5h again, the product finally obtaining is yellowish-brownThick liquid 12.5g, is PBTCA of the present invention.
Embodiment 2
In reactor, add 13.8g diethyl phosphite and 17.2g maleic diethylester, open condensation reflux unit, stirringMixing device rotating speed is 200r/min, slowly drips 4.8g catalyst A at agitator speed under the stirring condition that is 200r/min, treatsAfter temperature rise to 100 DEG C, react 1h. Then be cooled to 50 DEG C, add 10.0g ethyl acrylate, anti-under stirringAnswer 8h. Toward the catalyst B that adds 16mL in reactor, be warming up to 80 DEG C of heating hydrolysis 0.5h, the product finally obtaining againFor yellowish-brown thick liquid 26.5g, be PBTCA of the present invention.
Embodiment 3
In reactor, add 20.7g diethyl phosphite and 25.8g maleic diethylester, open condensation reflux unit, stirringMixing device rotating speed is 200r/min, slowly drips 7.2g catalyst A at agitator speed under the stirring condition that is 200r/min, treatsAfter temperature rise to 100 DEG C, react 1h. Then be cooled to 50 DEG C, add 15g ethyl acrylate, anti-under stirringAnswer 8h. Toward the catalyst B that adds 24mL in reactor, be warming up to 80 DEG C of heating hydrolysis 0.5h, the product finally obtaining againFor yellowish-brown thick liquid 40.0g, be PBTCA of the present invention.
Embodiment 4
In reactor, add 31.05g diethyl phosphite and 38.7g maleic diethylester, open condensation reflux unit, stirringMixing device rotating speed is 200r/min, slowly drips 10.8g catalyst A at agitator speed under the stirring condition that is 200r/min, treatsAfter temperature rise to 100 DEG C, react 1h. Then be cooled to 50 DEG C, add 22.5g ethyl acrylate, anti-under stirringAnswer 8h. Toward the catalyst B that adds 36mL in reactor, be warming up to 80 DEG C of heating hydrolysis 0.5h, the product finally obtaining againFor yellowish-brown thick liquid 62.5g, be PBTCA of the present invention.
Claims (2)
1. the preparation method of a low-phosphorus corrosion and scale inhibitor PBTCA. It is characterized in that adopting following steps to carry out:
A certain amount of diethyl phosphite and diethyl maleate are added in reactor, open condensation reflux unit, stirringMix under the stirring condition that device rotating speed is 200r/min and slowly to drip a certain amount of catalyst A, reaction after temperature rise to 100 DEG C1h. Then be cooled to 50 DEG C, add a certain amount of ethyl acrylate, under stirring, react 8h. In reactor, add againEnter a certain amount of catalyst B, be warming up to 80 DEG C of heating hydrolysis 0.5h, the product finally obtaining is yellowish-brown thick liquid, isPBTCA of the present invention.
2. the preparation method of low-phosphorus corrosion and scale inhibitor PBTCA according to claim 1. It is characterized in that: catalyst A isThe ethylenediamine of mass concentration 99%, catalyst B is the concentrated hydrochloric acid of mass concentration 37.5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510981542.6A CN105601668A (en) | 2015-12-24 | 2015-12-24 | Preparation method of low-phosphorous corrosion and scale inhibitor PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid) |
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| CN201510981542.6A CN105601668A (en) | 2015-12-24 | 2015-12-24 | Preparation method of low-phosphorous corrosion and scale inhibitor PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid) |
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| CN201510981542.6A Pending CN105601668A (en) | 2015-12-24 | 2015-12-24 | Preparation method of low-phosphorous corrosion and scale inhibitor PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105600955A (en) * | 2015-12-24 | 2016-05-25 | 常州大学 | Synthesis method and application of low-phosphorous corrosion and scale inhibitor |
| CN109336927A (en) * | 2018-10-26 | 2019-02-15 | 洪湖市泰科技有限公司 | A kind of preparation method of phosphine system reactive flame retardant monomer |
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|---|---|---|---|---|
| US4931586A (en) * | 1988-09-03 | 1990-06-05 | Bayer Aktiengesellschaft | Process for the continuous production of 2-phosphone-butane-1,2,4-tricarboxylic acid and alkali metal salts thereof |
| CN1173499A (en) * | 1997-09-03 | 1998-02-18 | 巴陵石油化工公司岳阳石油化工总厂 | Method for synthetizing 2-phosphonate butane-1,2,4-tricarboxylic acid |
| CN102030777A (en) * | 2010-11-29 | 2011-04-27 | 青岛大学 | Production method of green energy-saving 2-butane phosphonate-1,2,4-tricarboxylic acid |
| CN105600955A (en) * | 2015-12-24 | 2016-05-25 | 常州大学 | Synthesis method and application of low-phosphorous corrosion and scale inhibitor |
-
2015
- 2015-12-24 CN CN201510981542.6A patent/CN105601668A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931586A (en) * | 1988-09-03 | 1990-06-05 | Bayer Aktiengesellschaft | Process for the continuous production of 2-phosphone-butane-1,2,4-tricarboxylic acid and alkali metal salts thereof |
| CN1173499A (en) * | 1997-09-03 | 1998-02-18 | 巴陵石油化工公司岳阳石油化工总厂 | Method for synthetizing 2-phosphonate butane-1,2,4-tricarboxylic acid |
| CN102030777A (en) * | 2010-11-29 | 2011-04-27 | 青岛大学 | Production method of green energy-saving 2-butane phosphonate-1,2,4-tricarboxylic acid |
| CN105600955A (en) * | 2015-12-24 | 2016-05-25 | 常州大学 | Synthesis method and application of low-phosphorous corrosion and scale inhibitor |
Non-Patent Citations (1)
| Title |
|---|
| 韩应琳等: "2-膦酸丁烷-1,2,4-三羧酸的合成", 《工业水处理》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105600955A (en) * | 2015-12-24 | 2016-05-25 | 常州大学 | Synthesis method and application of low-phosphorous corrosion and scale inhibitor |
| CN109336927A (en) * | 2018-10-26 | 2019-02-15 | 洪湖市泰科技有限公司 | A kind of preparation method of phosphine system reactive flame retardant monomer |
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Application publication date: 20160525 |