JP3381273B2 - Antifouling agent for petroleum refining - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling agent for petroleum refining for preventing the adhesion of dirt on a petroleum refining apparatus. [0002] In the petroleum refining industry, refinement facilities have recently been advanced from the viewpoint of responding to environmental problems and increasing the production of white oil. The introduction of crackers, hydrodesulfurizers, catalytic crackers, and the like, or the severer operating conditions of these devices, are being promoted. Introduction of these devices or severer operating conditions results in the formation of sludge in residual oil obtained from these devices, causing problems such as fouling of heat exchangers and clogging of filters. When such a failure occurs, the operation of the apparatus is stopped and the operation of removing the contaminants is performed, but frequent operation of this operation leads to the stop of the plant. In order to avoid such a situation, the operating conditions are reduced or the devices are parallelized. However, these are very disadvantageous economically. [0003] In order to prevent the adherence of fouling substances, there have hitherto been proposed many methods of adding a fouling inhibitor to a feedstock. Examples of such an antifouling agent include an amide condensation product of a high molecular weight (molecular weight of 600 to 3000) monocarboxylic acid and an alkylene polyamine (Japanese Patent Publication No. 46-23504), ammonia (Japanese Patent Application Laid-Open No. 54-69106). , Polyalkyleneamine (JP-A-55-129490), polyoxyalkylene carbamate (JP-A-59-232170)
and so on. However, by adding these compounds to feedstocks such as crude oil, it is possible to prevent contamination to some extent, but it is still not enough. SUMMARY OF THE INVENTION An object of the present invention is to provide a high-performance antifouling agent for preventing the adhering of dirt on a heat exchanger and various processing apparatuses in a petroleum refining process. It is. Means for Solving the Problems As a result of intensive studies, the present inventors have found that an amide compound of alkylalkylenediamine is effective as an antifouling agent, and completed the present invention. That is, the present invention provides a compound represented by the following formula (A) and a compound represented by the formula (B) having a molar ratio of 2
/ 1/4/4 reaction alkylene alkylene
An antifouling agent for petroleum refining containing an amide compound of a diamine as an active ingredient . R ¹ COOH (A) R ² NH (CH ₂ ) _n NH ₂ (B) (R ¹ is a hydrocarbon group having 9 to 29 carbon atoms, R ² is a hydrocarbon group having 10 to 30 carbon atoms)
Wherein at least one of R ¹ and R ² is a saturated hydrocarbon group, and n is 2 to 6. The compound of the formula (A) which is a raw material of the antifouling agent of the present invention is a fatty acid wherein R ¹ is a hydrocarbon group having 9 to 29 carbon atoms, and R ¹ is a linear or branched saturated or unsaturated. Is a hydrocarbon group. Examples of the compound of the formula (A) include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melicic acid, oleic acid, and erucic acid. Yes, and also contain tallow fatty acid, hardened tallow fatty acid, hardened palm oil fatty acid, hardened palm oil fatty acid, hardened rapeseed oil fatty acid, coconut oil fatty acid, hardened fish oil fatty acid, further isomyristate isopalmitic acid, isostearic acid, isoarachinic acid, There are synthetic fatty acids such as isohexacosanoic acid. In the compound of the formula (B), R ² has 10 to 30 carbon atoms.
And n is an alkylalkylenediamine of 2 to 6. Examples of the compound of the formula (B) include dodecylethylenediamine, tetradecylpropylenediamine, hexadecylbutylenediamine, octadecylethylenediamine, eicosylhexenediamine, docosylpropylenediamine, tallowalkylpropylenediamine, hydrogenated rapeseed oil alkylpropylenediamine, oleylpropylenediamine and so on. When the compound of the formula (A) and the compound of the formula (B) are used in a molar ratio of 2/1 to 4/5 and reacted at, for example, 150 to 230 ° C. while distilling off the reaction water, the dirt of the present invention can be obtained. An inhibitor is obtained. Further, R ¹ of formula (A), at least one of R ² of formula (B) is a saturated hydrocarbon group. [0008] Outside the range of the above-mentioned limiting conditions, no sufficient stain prevention effect can be obtained. To prevent fouling using the petroleum refining antifouling agent of the present invention, for example, diluting the antifouling agent with an organic solvent to obtain a viscosity that is easy to handle, and continuously injecting 5 to 500 ppm of an effective component. Is preferred. If the injection amount is small, the effect of preventing contamination is not exhibited, and if it is too large, the effect is not improved, and the economical efficiency is deteriorated. A more preferable injection amount is 10 to 100 ppm. Taking the atmospheric distillation step of crude oil as an example, the injection location may be either on the crude oil side or on the residual oil side, but when adding to the crude oil side, it is preferable to inject at the outlet of the desalting tank, In the case of addition, it is preferable to inject into the suction side of the distillation column residual oil outlet pump. The antifouling agent for petroleum refining of the present invention effectively prevents the adhering of contaminants to the petroleum refining equipment such as the inner surface of a heat exchanger or a filter. Therefore, in various processing steps of the petroleum refining industry, crude oil, light naphtha, heavy naphtha, kerosene, gas oil, vacuum gas oil, vacuum residue, desulfurization residue,
By adding it to cracked residual oil or the like, the amount of deposits and deposits deposited can be significantly reduced. [0010] In particular, when added to the residual oil from a hydrodesulfurization unit or a catalytic cracking unit using atmospheric residual oil as a raw material, dirt in a heat exchanger and clogging of a filter are remarkably reduced. The frequency can be reduced, and the severity of the operating conditions of the device can be increased. The heavy oil purified by adding the antifouling agent of the present invention can also reduce dirt on heat exchangers and pipes when used in combustion equipment. Next, the present invention will be described in detail with reference to examples. [Stain Prevention Test] Evaluation of the stain preventive agent was performed according to ASTM (D16
61-64), with the following changes. The temperature of the heater section is changed from 180 ° C. to 320 ° C.
The cooling pipe of the channel was changed from glass to iron. A predetermined amount of the stain preventive agent shown in Table 1 was added to the sample oil, heated and dissolved at 80 ° C., tested, cooled to room temperature, and the cooling tube and the protective tube of the heater were washed with toluene, and then washed with a cloth. After wiping, the appearance was observed and evaluated according to the following criteria. Δ: Almost no change. Δ: Brown-black is slightly colored. ×: Brown to black, or tar-like deposits. The sample oil used in the test was desulfurized residual oil, and its properties are as follows. Density (g / cm ³ ) 0.9103 (JIS K-2249) Flash point (℃) 9.8 (JIS K-2265) Sulfur content (wt%) 0.18 (JIS K-2541) Kinematic viscosity (cSt / 50 ℃) 98.3 (JIS K-2283) Dry sludge (wt%) 0.49 (SMS 742) The results are shown in Table 2. [Table 1] (Note 1) “Emazol 871” Emery Ind. (Note 2) Isopalmitic acid Nissan Chemical Industries (Note 3) “HA18GT” Mitsubishi Kasei Kogyo (Note 4) Isostearic acid Nissan Chemical Industries (Note 5) Weight average molecular weight 900 [Table 2] The antifouling agent of the present invention did not give any deposits to the cooling tube and the protective tube, did not change, and exhibited an antifouling effect even at a low addition amount. The antifouling agent of the comparative example provided colored or tar-like deposits on the cooling tube and the protective tube.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C10L 1/22 C10G 7/00 F28F 19/00

Claims (1)

(57) [Claims] (1) A compound represented by the following formula (A) and a compound represented by the formula (B):
Amide compound of alkyl alkylenediamine which is a reaction product with a compound represented by the formula (1) at a molar ratio of 2/1 to 4/5
An antifouling agent for petroleum refining, comprising as an active ingredient . R ¹ COOH (A) R ² NH (CH ₂ ) _n NH ₂ (B) (R ¹ is a hydrocarbon group having 9 to 29 carbon atoms, R ² is a hydrocarbon group having 10 to 30 carbon atoms, and R ¹ , at least one of R ² is a saturated hydrocarbon group, n represents 2 to 6.)