CN101654628B

CN101654628B - Scale and corrosion inhibitor used for hydrogenation device and synthesis method thereof

Info

Publication number: CN101654628B
Application number: CN 200810030282
Authority: CN
Inventors: 罗将
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-08-20
Filing date: 2008-08-20
Publication date: 2013-03-20
Anticipated expiration: 2028-08-20
Also published as: CN101654628A

Abstract

The invention discloses a scale and corrosion inhibitor used for a hydrogenation device and a synthesis method thereof. The scale and corrosion inhibitor is characterized by comprising the following components in percentage by weight: A, 25 to 40 percent of film-forming amine compound; B, 10 to 20 percent of neutral amine mixture; C, 10 to 15 percent of dispersion component; and D, 10 to 40 percent of compound solvent. The synthesis method comprises the following steps: firstly, adding A and D, heating the mixture for 30 minutes under the condition of stirring, then adding the rest componentsinto the mixture respectively, and stirring the mixture for 2 hours to form the scale and corrosion inhibitor. When the adding amount of the scale and corrosion inhibitor is 5 to 15ppm of medium flow, the generation of corrosion and salt scale can be effectively inhibited; and the full water-soluble formulation of the scale and corrosion inhibitor is directly discharged along with washing, and has no adverse effect on subsequent oils.

Description

The anti-incrustation corrosion inhibitor and the synthetic method thereof that are used for hydrogenation unit

Technical field

The invention belongs to the chemical additive field, relate to a kind of inhibiter, relate in particular to a kind of anti-incrustation corrosion inhibitor for hydrogenation unit and synthetic method thereof.Prevent hydrogenation unit high-pressure air cooler and downstream line because the anti-incrustation corrosion inhibitor of the chemical corrosion that the fouling that causes of ammonia salt, the underdeposit corrosion that is caused by fouling and other corrosive medium cause.

Background technology

The oil hydrogenation technology is the important means of refining of petroleum products, upgrading and heavy oit pyrolysis processing.Its distinguishing feature is high temperature, high pressure, faces hydrogen, because the purpose of its technological process is the S that removes in the hydro carbons, and N, therefore the undesirable components elements such as Cl, O are attended by H ₂S, HCl, NH ₄Cl, NH ₄The formation of the compounds such as HS just exists more serious H in the high pressure position of reactive system and condensed downstream cooling system ₂S-HCl-NH ₃-H ₂O type corrosion, simultaneously high-pressure air cooler the relief outlet that descends most have very serious scale formation and the underdeposit corrosion that causes thus near pipe bottom and the downstream line of tube sheet.

According to the variation of development need and the petroleum products demand structure of China's oil industry, hydrocracking and refining complete-set applied technology ratio strengthen gradually.Simultaneously, the trend that the crude oil of processing becomes weight, high-sulfur, peracid is more and more serious, and this anticorrosion of equipment to hydrogenation unit is had higher requirement.

Refinery determines to adopt controls corrosion with this method of inhibiter, advantage easy to use, that consumption is few, cost is low, effective.Now both at home and abroad very many about the patent of inhibiter, but few to the fouling at Cooler in Hydro-processing place and the effective finding of underdeposit corrosion that causes thus.So in the urgent need to developing the anti-incrustation corrosion inhibitor that is fit to the Cooler in Hydro-processing position, fundamentally to solve the fouling corrosion problem of equipment and pipeline, guarantee equipment safety, steady, long-term operation operation.

CN200510023367.6 has reported a kind of anti-incrustation corrosion inhibitor for hydrogenation unit, and by polyoxy alkylene aminated compounds, multipolymer, tert-butyl phenol compound, homopolymer and aromatic hydrocarbon based the composition, wherein aromatic hydrocarbon based is toluene or dimethylbenzene.Although this patent can reach certain scale inhibitor effect, owing to contain the toxic organic compounds such as tert.-butyl phenol, toluene or dimethylbenzene in its composition, therefore there is the defective of easy contaminate environment, be not suitable for promoting the use of.

Summary of the invention

First purpose of the present invention is that existing anti-incrustation corrosion inhibitor is poisonous, the shortcoming of easy contaminate environment in order to overcome, and a kind of anti-incrustation corrosion inhibitor for hydrogenation unit is provided.

Second purpose of the present invention is for a kind of synthetic method of the anti-incrustation corrosion inhibitor for hydrogenation unit is provided.

First purpose of the present invention can reach by following embodiment:

Be used for the anti-incrustation corrosion inhibitor of hydrogenation unit, it is characterized in that being consisted of by following material component:

A, film forming class aminated compounds: 25-40% (wt%)

The mixture of B, neutrality amine: 10-20% (wt%)

C, dispersed component: 10-15% (wt%)

D, complex solvent: 10-40% (wt%)

Described film forming class aminated compounds can be polyoxy alkylene aminated compounds, and wherein the polyoxy alkylene is polyoxyethylene groups or polyoxypropylene base, and amine is an amine, diamines or polyamines; The mixture of described neutrality amine is polyethylene polyamine; Described dispersed component can be the tensio-active agents such as tetrem alkene triamine; Described complex solvent is ethanol: the mass ratio that deionization is purified waste water is the mixed solvent of 1:1-1:0.75.

The optimum content of described A component is 30-35% (wt%); The optimum content of B component is 15-20% (wt%); The optimum content of C component is 12-15% (wt%); The total content of described A, B, C three compounds is 50-65% (wt%), and optimum is 60-65% (wt%).

The applicable device of described anti-incrustation corrosion inhibitor is the hydrotreatment series process apparatus (comprising hydrofining, cracking etc.) of oil play; Applicable equipment and pipeline comprise high-pressure air cooler and upstream device and pipeline; Be applicable to because fouling and the corrosion that ammonia salt crystallization causes.

The add-on of described anti-incrustation corrosion inhibitor is the 5-15ppm of rate-of flow.

The physical and chemical index of described anti-incrustation corrosion inhibitor sees Table 1.

First purpose of the present invention can reach by following embodiment:

Be used for the synthetic method of the anti-incrustation corrosion inhibitor of hydrogenation unit, it is characterized in that comprising the steps:

1) takes by weighing in proportion each component, be ready to the agitator with the lifting/lowering temperature function;

2) in agitator, add A and D in proportion first, agitator is heated up, when the material temperature is warmed up to 80 ℃, continue to stir 30 minutes;

3) then in agitator, add B and C in proportion, continue to keep stirring 2 hours, can obtain described anti-incrustation corrosion inhibitor.

The present invention has following outstanding beneficial effect:

1, the anti-incrustation corrosion inhibitor of the present invention element such as containing metal not, complete water-soluble prescription, the inhibiter component can be discharged along with wash water directly arrives follow-up sewage, can not enter the oil phase system, follow-up oil product is had no adverse effects, have simultaneously good scale inhibition and dissemination, to the corrosive environment strong adaptability, in the scope of pH4-9, all can play the effect effect of good inhibition corrosion.

2, inhibiter of the present invention have that synthetic route is simple, raw material is cheap and easy to get, cost of manufacture is low, efficient, nontoxic, pollution-free, can not produce the effect of waste, and have easy to usely, loading system is invested the fireballing advantage of little enforcement.Only need to add a small amount of described dose can the establishment corrosion and the generation of salt crust, and to the character of installing the normal process product and following process process without features such as any adverse influences.

Embodiment

Below in conjunction with embodiment the present invention is further described, but embodiments of the present invention are not limited to this.

Reagent: required reagent is industrial rank in the test.

Instrument: petroleum products kinematic viscosity tester, SPH265-I; The petroleum products questionable points determinator, BSY-176; The open cup flash test device, BSY-101; The grease dropping point tester, SYD-4929A; The Sai Duolisi electronic balance, BS200-WE1; Closed electric furnace, ES-K; Digital display stainless steel air dry oven, GZX-9000; Electric blender, JB90-D; The digital display viscometer, NDJ-8S, stainless steel electrical distiller, 5L/H.

Embodiment 1

Taking by weighing 40 gram polyoxyethylene groups one amine compound and 20 gram deionizations purifies waste water and 20 gram ethanol, join in the agitator, treat that temperature rises to 80 ℃, in situation about stirring, kept this temperature 30 minutes, then take by weighing respectively 10 gram polyethylene polyamines and 10 gram tetrem alkene triamines, join in the agitator, 80 ℃ of constant temperature were kept this temperature 2 hours in situation about stirring.Naturally cool to room temperature, can obtain anti-incrustation corrosion inhibitor.

Embodiment 2

Taking by weighing 30 gram polyoxyethylene groups one amine compound and 20 gram deionizations purifies waste water and 20 gram ethanol, join in the agitator, treat that temperature rises to 80 ℃, in situation about stirring, kept this temperature 30 minutes, then take by weighing respectively 15 gram polyethylene polyamines and 15 gram tetrem alkene triamines, join in the agitator, 80 ℃ of constant temperature were kept this temperature 2 hours in situation about stirring.Naturally cool to room temperature, can obtain anti-incrustation corrosion inhibitor.

Embodiment 3

Taking by weighing 35 gram polyoxyethylene groups diamine compounds and 15 gram deionizations purifies waste water and 20 gram ethanol, join in the agitator, treat that temperature rises to 80 ℃, in situation about stirring, kept this temperature 30 minutes, then take by weighing respectively 18 gram polyethylene polyamines and 12 gram tetrem alkene triamines, join in the agitator, 80 ℃ of constant temperature were kept this temperature 2 hours in situation about stirring.Naturally cool to room temperature, can obtain anti-incrustation corrosion inhibitor.

Analyze erosion rate by the iron ion of analyzing follow-up sour water and find that the iron ion before the injecting is annotated behind the inhibiter of the present invention on average at 5-6ppm, iron ion is controlled at about 1ppm, and basic corrosion inhibition rate is at 80-90%.

Through test, certain first cycle of operation of refinery VGO once was forced to twice processing of stopping work because obstruction and the etching problem that ammonia salt crystallization causes appears in high-pressure air cooler and the downstream line of reactive system.Maintenance is found serious fouling latch up phenomenon to have occurred in the high-pressure air cooler tube bank, find seriously corroded by the equipment thickness measuring, second cycle of operation, the proportioning of having annotated is operation 2 years behind the anti-incrustation corrosion inhibitor 10ppm of the present invention of A:B:C:D=35:18:12:35, do not occur equipment corrosion in this cycle and stop up the shut-down that seriously causes and the normal processing amount phenomenon that affects device, annotate simultaneously and do not find follow-up sewage index exceeding standard behind this inhibiter, each index normal operation of apparatus system, do not have between turn(a)round simultaneously serious the obstruction and the serious phenomenon of corrosion thinning of tube bank that a upper cycle occurs to occur, well solved fouling obstruction and the etching problem of high-pressure air cooler.

Table 1 is the physical and chemical index regulation of product.

Table 1 physical and chemical index

Project	Index	Analytical procedure
			Outward appearance	Light yellow to tawny liquid	Range estimation
Density (20 ℃) g/cm ³	0.95-1.15	GB/T4472-1984
			Flash-point (remain silent cup) ℃	>50	ASTM?D93
Condensation point ℃	≦0	ASTM?D97
			Kinematic viscosity (40 ℃) mm ²/s	≦25	ASTM?D445

Claims

1. anti-incrustation corrosion inhibitor that is used for hydrogenation unit is characterized in that:

1) composition and proportioning are as follows:

A, film forming class aminated compounds: 25-40%(wt%)

The mixture of B, neutrality amine: 10-20%(wt%)

C, dispersed component: 10-15%(wt%)

D, complex solvent: 10-40%(wt%);

Each component concentration percentage ratio sum is 100%;

2) described film forming class aminated compounds is polyoxy alkylene aminated compounds, and wherein the polyoxy alkylene is polyoxyethylene groups or polyoxypropylene base, and amine is an amine, diamines or polyamines; The mixture of described neutrality amine is polyethylene polyamine; Described dispersed component is tetrem alkene triamine tensio-active agent; Described complex solvent is ethanol; The mass ratio that deionization is purified waste water is the mixed solvent of 1:1-1:0.75.

2. the anti-incrustation corrosion inhibitor for hydrogenation unit according to claim 1, it is characterized in that: described A component concentration is 30-35%; The B component concentration is 15-20%; The C component concentration is 12-15%; The total content of A, B, C three compounds is 50-65%.

3. the anti-incrustation corrosion inhibitor for hydrogenation unit according to claim 2, it is characterized in that: the total content of described A, B, C three compounds is 60-65%.

4. the anti-incrustation corrosion inhibitor for hydrogenation unit according to claim 1 is characterized in that: the applicable device of described anti-incrustation corrosion inhibitor is the hydrotreatment series process apparatus of oil play, and described hydrotreatment series process comprises hydrofining, cracking; Applicable equipment and the pipeline of described anti-incrustation corrosion inhibitor comprises high-pressure air cooler and upstream device and pipeline; Described anti-incrustation corrosion inhibitor is applicable to because fouling and the corrosion that ammonia salt crystallization causes.

5. the anti-incrustation corrosion inhibitor for hydrogenation unit according to claim 1, it is characterized in that: the add-on of described anti-incrustation corrosion inhibitor is the 5-15ppm of rate-of flow.

6. the synthetic method of the anti-incrustation corrosion inhibitor for hydrogenation unit as claimed in claim 1 is characterized in that may further comprise the steps:

1) takes by weighing in proportion each component, in agitator, add first A component and D component, when being warmed up to 80 ℃, in situation about stirring, continue 30 minutes;

2) then add respectively B component and C component, keep stirring 2 hours, namely obtain described anti-incrustation corrosion inhibitor.