CN101525750B - Use of compound inhibitors for restricting carbon steel corrosion in methanol solution - Google Patents
Use of compound inhibitors for restricting carbon steel corrosion in methanol solution Download PDFInfo
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Abstract
The invention relates to an organic compound inhibitor and an inorganic compound inhibitor for restricting carbon steel corrosion in a methanol solution and the application thereof. The organic compound inhibitor comprises zinc salt, hydroxyl phosphono-acetic acid and any one or two of other phosphonic acid, and the inorganic compound inhibitor comprises zinc salt, molybdate and at least one hydrophosphate. When used for treating the methanol solution, the organic compound inhibitor and the inorganic compound inhibitor can prevent the methanol solution from corroding carbon steel equipment, greatly decreases the corrosion speed of carbon steel, increases the inhibition efficiency; in addition, the organic compound inhibitor and the inorganic compound inhibitor have simple operation, convenience, rapidness, safety and efficiency and can not generate adverse influence on the further separation and the recycle of methanol.
Description
The application is 200510135159.5 divides an application, and its applying date is: on December 29th, 2005, denomination of invention is: a kind ofly be used to suppress methanol solution medium carbon steel corrosive composite corrosion inhibitor and application thereof.
Technical field
The present invention relates to a kind of be used to suppress methanol solution medium carbon steel corrosive composite corrosion inhibitor and application thereof, especially for suppressing methanol solution medium carbon steel corrosive organic composite corrosion inhibitor and inorganic compounding inhibiter and application thereof.
Background technology
As a kind of important gasoline octane rating improving agent, MTBE has obtained using widely at high grade white gasoline production field.MTBE not only can increase the oxygen level of gasoline, can also promote the clean burning of gasoline, reduces the pollution of automobile hazardous emission.Simultaneously, MTBE can also cracking produce high-purity isobutylene under the effect of catalyzer, and is used for the production of isoprene-isobutylene rubber as raw material.
In the building-up process of MTBE,, produce the thick product of MTBE with by-product carbon-4 cut behind iso-butylene, dimethyl formamide (DMF) extracting divinyl or the acetonitrile extracting divinyl and methyl alcohol reaction.Through the rectifying separation to MTBE, remaining iso-butylene or C-4-fraction and methyl alcohol will just can make the methanol loop utilization through the extracting and separating of water.In extraction with reclaim in the process of methyl alcohol, with the carbon steel be the methanol extraction tower, methanol distillation column of material and therebetween heat-exchange equipment contact with methanol solution, more serious corrosion phenomenon has taken place.Produce in the high-purity isobutylene process in the MTBE cracking, the MTBE cracking generates iso-butylene and methyl alcohol.Thick product also need be that extraction agent separates it with water, realizes the refining of iso-butylene, and reclaims methyl alcohol.In washing with reclaim in the process of methyl alcohol, with the carbon steel be the water wash column, methanol rectifying tower of material and therebetween heat-exchange equipment contact with methanol solution, serious corrosion phenomenon has also taken place.Prior art also is not used to inhibiter to suppress the corrosion of methanol solution medium carbon steel.
Summary of the invention
The object of the present invention is to provide a kind of organic composite corrosion inhibitor, to solve the corrosion of Carbon Steel that contacts with methanol solution.
Another object of the present invention provides a kind of inorganic compounding inhibiter, to solve the corrosion of Carbon Steel that contacts with methanol solution.
A further object of the present invention is organic composite corrosion inhibitor of the present invention and inorganic compounding inhibiter are used to suppress the corrosion of methanol solution medium carbon steel.
For achieving the above object, the invention provides a kind of organic composite corrosion inhibitor, it consists of zinc salt, hydroxyethylidene diphosphonic acid guanidine-acetic acid and one or both optional other organic phospho acids.
Organic composite corrosion inhibitor of the present invention is applicable to the corrosion of carbon steel that inhibition contacts with methanol solution.
Other organic phospho acid of the present invention is different from the hydroxyethylidene diphosphonic acid guanidine-acetic acid, be selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 2-phosphonate group-1,2,4-butane tricarboxylate, diethylene triamine pentamethylene phosphonic, Amino Trimethylene Phosphonic Acid and ethylene diamine tetra methylene phosphonic acid are preferably 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 2-phosphonate group-1,2,4-butane tricarboxylate and diethylene triamine pentamethylene phosphonic, more preferably 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 2-phosphonate group-1,2, the 4-butane tricarboxylate.
Zinc salt of the present invention is selected from zinc sulfate and zinc chloride, is preferably Zinc vitriol.
Organic composite corrosion inhibitor of the present invention is with respect to the amount of water in the handled methanol solution, the effective concentration of hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content) is 1.0～10.0mg/L, the effective concentration of organic phospho acid (in active matter content) is 0～10.0mg/L, and the effective concentration of zinc salt is (with Zn
2+Meter) be 1.0～10.0mg/L, the effective concentration of preferred hydroxyethylidene diphosphonic acid guanidine-acetic acid is 2.0～6.0mg/L, and the effective concentration of organic phospho acid is 1.0～10.0mg/L, and the effective concentration of zinc salt is 2.0～6.0mg/L.
When preparing organic composite corrosion inhibitor of the present invention, the reinforced order of every kind of component is unimportant.Zinc salt, hydroxyethylidene diphosphonic acid guanidine-acetic acid and other organic phospho acid and water are made into a kind of compound organic corrosion inhibitor solution by predetermined mixed.In the preparation process of compound organic inhibitor, also can add a spot of acid (as dilute sulphuric acid, dense or dilute hydrochloric acid etc.), to promote the dissolving of zinc salt, to obtain the uniform solution of desired concn as early as possible.
The present invention also provides a kind of methanol solution medium carbon steel corrosive inorganic compounding inhibiter that is used to suppress, and it consists of molybdate, zinc salt and at least a hydrophosphate.
Inorganic compounding inhibiter of the present invention is applicable to the corrosion of carbon steel that inhibition contacts with methanol solution.
Zinc salt of the present invention is selected from zinc sulfate and zinc chloride, is preferably Zinc vitriol; Described molybdate is Sodium orthomolybdate or potassium molybdate, is preferably two molybdic acid hydrate sodium; Described hydrophosphate is selected from potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, Sodium phosphate dibasic, preferably from potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC.
Inorganic inhibitor of the present invention is with respect to the amount of water in the handled methanol solution, and the effective concentration of hydrophosphate is (with PO
4 3-Meter) be 1.0～10.0mg/L, the effective concentration of zinc salt is (with Zn
2+Meter) be 1.0～20.0mg/L, the effective concentration of molybdate is (with MO
4 2-Meter) be 1.0～50.0mg/L, the effective concentration of preferably phosphoric acid hydrogen salt is 1.0～5.0mg/L, and the effective concentration of zinc salt is 1.0～10.0mg/L, and the effective concentration of molybdate is 1.0～20.0mg/L.
When preparing inorganic compounding inhibiter of the present invention, produce precipitation when preventing that hydrophosphate and molybdate are mixed into highly concentrated solution, hydrophosphate, zinc salt and water and molybdate and water are made into two kinds of corrosion inhibitor solutions by predetermined mixed respectively, and mutual group becomes inorganic compounding inhibiter of the present invention.In the mixing solutions preparation process of hydrophosphate and zinc salt, also can add a spot of acid (as dilute sulphuric acid, dense or dilute hydrochloric acid etc.), to promote the dissolving of zinc salt etc., to obtain the uniform solution of desired concn as early as possible.During use, with two kinds of corrosion inhibitor solutions successively or add simultaneously in the methanol solution, it is unimportant to add order.
When using organic composite corrosion inhibitor of the present invention and inorganic compounding inhibiter, described composite corrosion inhibitor or described inorganic compounding inhibiter are joined in the methanol solution by prescribed concentration, can prevent the corrosion of carbon steel that contacts with methanol solution.
The mass percentage concentration of methanol solution of the present invention is 10%～98%, be preferably 10-60%, 10-30% more preferably, and the temperature of methanol solution is 30～90 ℃, is preferably 30～60 ℃, more preferably 30～50 ℃.
Methanol solution of the present invention is when being raw material production methyl alkyl ether with hydrocarbon and methyl alcohol, methanol extraction tower, methanol distillation column and the methanol solution in the heat-exchange equipment therebetween, perhaps when being the raw material production iso-butylene with methyl alkyl ether, water wash column, methanol rectifying tower and the methanol solution in the heat-exchange equipment therebetween; Be preferably when being the raw material production methyl tertiary butyl ether with mixed c 4 cut or isoolefine and methyl alcohol, methanol extraction tower, methanol distillation column and the methanol solution in the heat-exchange equipment therebetween, perhaps when being the raw material production iso-butylene with MTBE, water wash column, methanol rectifying tower and the methanol solution in the heat-exchange equipment therebetween.
When compound organic inhibitor of the present invention is used to handle methanol solution, can solve the corrosion that methanol solution causes carbon steel equipment, Corrosion rate in Carbon Steel is reduced greatly, simultaneously corrosion inhibition rate is also higher, and it is simple to operate, convenient and swift, safe and effective, can the further separation and the recycling of methyl alcohol do not had a negative impact.
When compound organic inhibitor of the present invention is used to handle methanol solution, can solve methanol solution, Corrosion rate in Carbon Steel be reduced greatly, simultaneously corrosion inhibition rate is also higher the corrosion that carbon steel equipment causes.And simple to operate, convenient and swift, safe and effective, can the further separation and the recycling of methyl alcohol do not had a negative impact.
Embodiment
The following examples will help to describe in detail the present invention, but not limit to its scope.
The rotary hanging plate weight-loss method is rotated coupon corrosion test in " water coolant analysis and the test method " that the following examples 1～6 are all write according to production department of China PetroChemical Corporation and development division (1993, general petrochemical works, Anqing information center publishes).Test lacing film material is the 20# carbon steel, and test temperature is 40 ℃, the test piece rotating speed be 75rpm (rev/min), test period is 72h.Test is 15% (concentration expressed in percentage by weight) with the concentration of methanol solution, and the water quality of water sees Table 1 in the methanol solution.
The table 1 test water quality of water in the methanol solution
The analytical procedure of water quality is with reference to " water coolant analysis and test method ".In not adding the blank methanol solution of inhibiter, the average corrosion rate of carbon steel reaches 1.1823mm/a.Organic composite corrosion inhibitor embodiment:
Embodiment 1
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content and be 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid 4.0g, be dissolved in the 50.0g water; Take by weighing the 8.8g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 35.2g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 2mg/L and 2mg/L.
Embodiment 2
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content and be 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid 8.0g, be dissolved in the 50.0g water; Take by weighing the 8.8g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 31.2g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L and 2mg/L.
Embodiment 3
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content and be 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid 8.0g, be dissolved in the 40.0g water; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 32.3g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L and 4mg/L.
Embodiment 4
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content and be 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid 16.0g, be dissolved in the 30.0g water; Take by weighing the 35.3g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 16.7g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 8mg/L and 8mg/L.
Embodiment 5
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content and be hydroxyethylidene diphosphonic acid guanidine-acetic acid and each 4.0g of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of 50%, be dissolved in the 50.0g water; Take by weighing the 8.8g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 31.2g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 2mg/L, 2mg/L and 2mg/L.
Embodiment 6
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% hydroxyethylidene diphosphonic acid base and acetate 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 8.0g and 4.0g, be dissolved in the 50.0g water; Take by weighing the 8.8g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 27.2g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L, 2mg/L and 2mg/L.
Embodiment 7
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid and 2-phosphonate group-1,2,4-butane tricarboxylate 8.0g and 4.0g are dissolved in the 50.0g water; Take by weighing the 13.2g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 22.8g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content), 2-phosphonate group-1,2,4-butane tricarboxylate (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L, 2mg/L and 3mg/L.
Embodiment 8
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be hydroxyl phosphino-acetate and each 6.0g of diethylene triamine pentamethylene phosphonic of 50%, be dissolved in the 40.0g water; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 28.3g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content), diethylene triamine pentamethylene phosphonic (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 3mg/L, 3mg/L and 4mg/L.
Embodiment 9
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid and Amino Trimethylene Phosphonic Acid 8.0g and 4.0g, be dissolved in the 40.0g water; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 28.3g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content), Amino Trimethylene Phosphonic Acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L, 2mg/L and 4mg/L.
Embodiment 10
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be hydroxyethylidene diphosphonic acid guanidine-acetic acid and each 6.0g of ethylene diamine tetra methylene phosphonic acid of 50%, be dissolved in the 40.0g water; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 28.3g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content), ethylene diamine tetra methylene phosphonic acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 3mg/L, 3mg/L and 4mg/L.
Embodiment 11
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and 2-phosphonate group-1,2,4-butane tricarboxylate 8.0g, 4.0g and 4.0g are dissolved in the 40.0g water; Take by weighing the 13.2g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 28.8g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content), 2-phosphonate group-1,2,4-butane tricarboxylate (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L, 2mg/L, 2mg/L and 3mg/L.
Embodiment 12
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and Amino Trimethylene Phosphonic Acid 8.0g, 4.0g and 4.0g, be dissolved in the 40.0g water; Take by weighing the 8.8g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 33.2g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, the effective concentration of hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content), Amino Trimethylene Phosphonic Acid (in active matter content) and Zinc vitriol (in Zn2+) is respectively 4mg/L, 2mg/L, 2mg/L and 2mg/L.
Comparative Examples 1
Preparation composite corrosion inhibitor 100g.
Take by weighing active matter content and be 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 8.0g, be dissolved in the 50.0g water; Take by weighing the 8.8g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 31.2g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L and 2mg/L.
Comparative Examples 2
Preparation composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and 2-phosphonate group-1,2,4-butane tricarboxylate 8.0g and 4.0g are dissolved in the 40.0g water; Take by weighing the 8.8g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 37.2g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content), 2-phosphonate group-1,2,4-butane tricarboxylate (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L, 2mg/L and 2mg/L.
Comparative Examples 3
Preparation composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and Amino Trimethylene Phosphonic Acid 12.0g and 4.0g, be dissolved in the 40.0g water; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 24.3g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content), Amino Trimethylene Phosphonic Acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 6mg/L, 2mg/L and 4mg/L.
Comparative Examples 4
Preparation organic composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 2-phosphonate group-1,2,4-butane tricarboxylate and Amino Trimethylene Phosphonic Acid 8.0g, 4.0g and 4.0g are dissolved in the 40.0g water; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 24.3g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content), 2-phosphonate group-1,2,4-butane tricarboxylate (in active matter content), Amino Trimethylene Phosphonic Acid (in active matter content) and Zinc vitriol are (with Zn
2+Meter) effective concentration is respectively 4mg/L, 2mg/L, 2mg/L and 4mg/L.
Comparative Examples 5
Preparation composite corrosion inhibitor 100g.
Take by weighing active matter content and be hydroxyethylidene diphosphonic acid guanidine-acetic acid and each 8.0g of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid of 50%, be dissolved in the 84.0g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, the effective concentration of hydroxyethylidene diphosphonic acid guanidine-acetic acid (in active matter content) and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content) is respectively 4mg/L and 4mg/L.
Comparative Examples 6
Preparation composite corrosion inhibitor 100g.
Take by weighing active matter content respectively and be 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 2-phosphonate group-1,2,4-butane tricarboxylate and Amino Trimethylene Phosphonic Acid 4.0g, 8.0g and 8.0g are dissolved in the 80.0g water, stir, and promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (in active matter content), 2-phosphonate group-1,2, the effective concentration of 4-butane tricarboxylate (in active matter content) and Amino Trimethylene Phosphonic Acid (in active matter content) is respectively 2mg/L, 4mg/L and 4mg/L.
Be rotated coupon corrosion test by the above-mentioned concentration that adds, corrosion speed and corrosion inhibition rate see Table 2.
The corrosion mitigating effect of organic composite corrosion inhibitor in table 2 methanol solution
The embodiment of inorganic compounding anti-incrustation corrosion inhibitor:
Embodiment 1
Preparation inhibiter 100g.
Take by weighing the 2.9g potassium primary phosphate and add in the 47.4g water, stir and make it dissolving; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved, promptly obtain inhibiter A agent 70g; Take by weighing 6.1g two molybdic acid hydrate sodium and add in the 23.9g water, stir and make it dissolving, promptly obtain inhibiter B agent 30g; A agent and B agent add up to 100g.
When adding in methanol solution respectively by the concentration of 70mg/L and 30mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, potassium primary phosphate is (with PO
4 3-Meter), Zinc vitriol is (with Zn
2+The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 2mg/L, 4mg/L and 4mg/L.
Embodiment 2
Preparation inhibiter 100g.
Take by weighing the 1.3g SODIUM PHOSPHATE, MONOBASIC and add in the 30.2g water, stir and make it dissolving; Take by weighing the 26.5g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved, promptly obtain inhibiter A agent 60g; Take by weighing 12.1g two molybdic acid hydrate sodium and add in the 27.9g water, stir and make it dissolving, promptly obtain inhibiter B agent 40g; A agent and B agent add up to 100g.
When adding in methanol solution respectively by the concentration of 60mg/L and 40mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, SODIUM PHOSPHATE, MONOBASIC is (with PO
4 3-Meter), Zinc vitriol is (with Zn
2+The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 1mg/L, 6mg/L and 8mg/L.
Embodiment 3
Preparation inhibiter 100g.
Take by weighing the 5.5g dipotassium hydrogen phosphate and add in the 34.8g water, stir and make it dissolving; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved, promptly obtain inhibiter A agent 60g; Take by weighing 18.2g two molybdic acid hydrate sodium and add in the 21.8g water, stir and make it dissolving, promptly obtain inhibiter B agent 40g; A agent and B agent add up to 100g.
When adding in methanol solution respectively by the concentration of 60mg/L and 40mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, dipotassium hydrogen phosphate is (with PO
4 3-Meter), Zinc vitriol is (with Zn
2+The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 3mg/L, 4mg/L and 12mg/L.
Embodiment 4
Preparation inhibiter 100g.
Take by weighing the 11.5g potassium primary phosphate and add in the 26.2g water, stir and make it dissolving; Take by weighing the 35.3g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved, promptly obtain inhibiter A agent 75g; Take by weighing 9.1g two molybdic acid hydrate sodium and add in the 15.9g water, stir and make it dissolving, promptly obtain inhibiter B agent 25g; A agent and B agent add up to 100g.
When adding in methanol solution respectively by the concentration of 75mg/L and 25mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, potassium primary phosphate is (with PO
4 3-Meter), Zinc vitriol is (with Zn
2+The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 8mg/L, 8mg/L and 6mg/L.
Embodiment 5
Preparation inhibiter 200g.
Take by weighing the 2.9g potassium primary phosphate and add in the 37.4g water, stir and make it dissolving; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved, promptly obtain inhibiter A agent 60g; Take by weighing 60.5g two molybdic acid hydrate sodium and add in the 79.5g water, stir and make it dissolving, promptly obtain inhibiter B agent 140g; A agent and B agent add up to 200g.
When adding in methanol solution respectively by the concentration of 60mg/L and 140mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, potassium primary phosphate is (with PO
4 3-Meter), Zinc vitriol is (with Zn
2+The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 2mg/L, 4mg/L and 40mg/L.
Embodiment 6
Preparation inhibiter 200g.
Take by weighing the 5.7g potassium primary phosphate and add in the 71.7g water, stir and make it dissolving; Take by weighing the 70.6g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved, promptly obtain inhibiter A agent 150g; Take by weighing 6.1g two molybdic acid hydrate sodium and add in the 43.9g water, stir and make it dissolving, promptly obtain inhibiter B agent 50g; A agent and B agent add up to 200g.
When adding in methanol solution respectively by the concentration of 150mg/L and 50mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, dipotassium hydrogen phosphate is (with PO
4 3-Meter), Zinc vitriol is (with Zn
2+The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 4mg/L, 16mg/L and 4mg/L.
Embodiment 7
Preparation inhibiter 100g.
Take by weighing 2.9g potassium primary phosphate and 1.8g dipotassium hydrogen phosphate and add in the 45.6g water, stir and make it dissolving; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved, promptly obtain inhibiter A agent 70g; Take by weighing 12.1g two molybdic acid hydrate sodium and add in the 17.9g water, stir and make it dissolving, promptly obtain inhibiter B agent 30g; A agent and B agent add up to 100g.
When adding in methanol solution respectively by the concentration of 70mg/L and 30mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, potassium primary phosphate is (with PO
4 3-Meter), dipotassium hydrogen phosphate is (with PO
4 3-Meter), Zinc vitriol is (with Zn
2+The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 2mg/L, 1mg/L, 4mg/L and 8mg/L.
Comparative Examples 1
Preparation inhibiter 100g.
Take by weighing the 2.8g potassium primary phosphate and add in the 50.0g water, stir and make it dissolving; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 27.5g water, stir, promptly obtain required 100g inhibiter.
When adding in methanol solution by the concentration of 100mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, potassium primary phosphate is (with PO
4 3-The meter) and Zinc vitriol (with Zn
2+Meter) effective concentration is respectively 2mg/L and 4mg/L.
Comparative Examples 2
Preparation inhibiter 150g.
Take by weighing 18.2g two molybdic acid hydrate sodium and add in the 50.0g water, stir and make it dissolving; Take by weighing the 26.5g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved; In above-mentioned solution, add 53.3g water, stir, promptly obtain required 150g inhibiter.
When adding in methanol solution by the concentration of 150mg/L with the inhibiter for preparing, calculate with the water yield in the methanol solution, two molybdic acid hydrate sodium are (with MoO
4 2-The meter) and Zinc vitriol (with Zn
2+Meter) effective concentration is respectively 12mg/L and 6mg/L.
Comparative Examples 3
Preparation inhibiter 100g.
Take by weighing the 2.8g potassium primary phosphate and add in the 47.2g water, stir and make it dissolving, promptly obtain inhibiter A agent 50g; Take by weighing 12.1g two molybdic acid hydrate sodium and add in the 37.9g water, stir and make it dissolving, promptly obtain inhibiter B agent 50g; A agent and B agent add up to 100g.。
When adding in methanol solution respectively by the concentration of 50mg/L and 50mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, potassium primary phosphate is (with PO
4 3-The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 2mg/L and 8mg/L.
Comparative Examples 4
Preparation inhibiter 100g.
Take by weighing the 3.5g tertiary sodium phosphate and add in the 46.8g water, stir and make it dissolving; Take by weighing the 17.7g Zinc vitriol and add in the above-mentioned solution, and add 1: 3 sulfuric acid 2.0g, Zinc vitriol is fully dissolved, promptly obtain inhibiter A agent 70g; Take by weighing 12.1g two molybdic acid hydrate sodium and add in the 17.9g water, stir and make it dissolving, promptly obtain inhibiter B agent 30g; A agent and B agent add up to 100g.
When adding in methanol solution respectively by the concentration of 70mg/L and 30mg/L with the inhibiter A agent for preparing and B agent, calculate with the water yield in the methanol solution, tertiary sodium phosphate is (with PO
4 3-Meter), Zinc vitriol is (with Zn
2+The meter) and two molybdic acid hydrate sodium (with MoO
4 2-Meter) effective concentration is respectively 2mg/L, 4mg/L and 8mg/L.
Be rotated coupon corrosion test by the above-mentioned concentration that adds, corrosion speed and corrosion inhibition rate see Table 3.
The corrosion mitigating effect of inorganic compounding inhibiter in table 3 methanol solution
Claims (9)
1. the purposes of inorganic compounding inhibiter, it is characterized in that the inorganic compounding inhibiter is joined in the methanol solution, with the corrosion of carbon steel that prevents to contact with methanol solution, wherein said inorganic compounding inhibiter consist of zinc salt, molybdate and at least a hydrophosphate, with respect to the amount of water in the handled methanol solution, the effective concentration of hydrophosphate is with PO
4 3-Count 1.0～10.0mg/L, the effective concentration of zinc salt is with Zn
2+Count 1.0～20.0mg/L, the effective concentration of molybdate is with MO
4 2-Count 1.0～50.0mg/L.
2. purposes according to claim 1 is characterized in that described zinc salt is selected from zinc sulfate and zinc chloride; Described molybdate is Sodium orthomolybdate or potassium molybdate; Described hydrophosphate is selected from potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, Sodium phosphate dibasic.
3. according to the purposes of the described inorganic compounding inhibiter of claim 2, it is characterized in that described zinc salt is a Zinc vitriol; Described molybdate is two molybdic acid hydrate sodium; Described hydrophosphate is selected from potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC.
4. purposes according to claim 1, it is characterized in that amount with respect to water in the handled methanol solution, the effective concentration of hydrophosphate is 1.0～5.0mg/L, and the effective concentration of zinc salt is 1.0～10.0mg/L, and the effective concentration of molybdate is 1.0～20.0mg/L.
5. according to each described purposes of claim 1-4, the mass percentage concentration that it is characterized in that methanol solution is 10%～15%, and the temperature of methanol solution is 30～90 ℃.
6. according to each described purposes of claim 1-4, it is characterized in that methanol solution is when being raw material production methyl alkyl ether with hydrocarbon and methyl alcohol, methanol extraction tower, methanol distillation column and the methanol solution in the heat-exchange equipment therebetween, perhaps when being the raw material production iso-butylene with methyl alkyl ether, water wash column, methanol rectifying tower and the methanol solution in the heat-exchange equipment therebetween.
7. purposes according to claim 5, it is characterized in that methanol solution is when being raw material production methyl alkyl ether with hydrocarbon and methyl alcohol, methanol extraction tower, methanol distillation column and the methanol solution in the heat-exchange equipment therebetween, perhaps when being the raw material production iso-butylene with methyl alkyl ether, water wash column, methanol rectifying tower and the methanol solution in the heat-exchange equipment therebetween.
8. purposes according to claim 6, it is characterized in that methanol solution is when being the raw material production methyl tertiary butyl ether with mixed c 4 cut or isoolefine and methyl alcohol, methanol extraction tower, methanol distillation column and the methanol solution in the heat-exchange equipment therebetween, perhaps when being the raw material production iso-butylene with MTBE, water wash column, methanol rectifying tower and the methanol solution in the heat-exchange equipment therebetween.
9. purposes according to claim 7, it is characterized in that methanol solution is when being the raw material production methyl tertiary butyl ether with mixed c 4 cut or isoolefine and methyl alcohol, methanol extraction tower, methanol distillation column and the methanol solution in the heat-exchange equipment therebetween, perhaps when being the raw material production iso-butylene with MTBE, water wash column, methanol rectifying tower and the methanol solution in the heat-exchange equipment therebetween.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100556A (en) * | 1986-02-07 | 1988-01-27 | 佳能株式会社 | Light receiving element |
| CN2177841Y (en) * | 1993-11-30 | 1994-09-21 | 茹春浩 | Sealing packing |
| JP2003017019A (en) * | 2001-06-29 | 2003-01-17 | Sony Corp | Case |
| CN1491907A (en) * | 2002-10-23 | 2004-04-28 | 中国石油化工股份有限公司北京燕山分 | Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water |
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2005
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100556A (en) * | 1986-02-07 | 1988-01-27 | 佳能株式会社 | Light receiving element |
| CN2177841Y (en) * | 1993-11-30 | 1994-09-21 | 茹春浩 | Sealing packing |
| JP2003017019A (en) * | 2001-06-29 | 2003-01-17 | Sony Corp | Case |
| CN1491907A (en) * | 2002-10-23 | 2004-04-28 | 中国石油化工股份有限公司北京燕山分 | Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water |
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