WO2005073277A1

WO2005073277A1 - Substituted polyethylene polyamines, method of their preparation and their use

Info

Publication number: WO2005073277A1
Application number: PCT/SK2005/000002
Authority: WO
Inventors: Milan Kucera; Magdalena Harustakova; Frantisek Masarovic
Original assignee: Slovnaft Vurup, A.S.
Priority date: 2004-01-30
Filing date: 2005-01-31
Publication date: 2005-08-11
Also published as: SK752004A3; SK286537B6

Abstract

Subject of the invention are substituted polyethylene polyamines having general formula (I), method of their preparation and their use as additives inhibiting, or limiting the formation of deposits in the process of cracking of hydrocarbon residues, which simultaneously prevent the formation of precursors of coke, especially asphaltenes, and bind free radicals affecting mainly the stability of products during their separation and storage.

Description

Description Substituted polyethylene polyamines, method of their preparation and their use

Technical field

[0001] The invention relates to substituted polyethylene polyamines, method of their preparation and their use as inhibitors of formation of resins and coke in pyrolysis processes, where they form undesired deposits in piping of pyrolysis furnaces during thermal cracking of hydrocarbon residues, such as primary vacuum residues, vacuum residues from hydrogenation cracking, non-converted oils from the process of hydrogenation cracking, and also various distillation layers of primary vacuum distillates and distillates from the process of hydrogenation cracking and non-converted fractions from the process of fluid catalytic cracking in processing of petroleum.

Background art [0002] The fouling of piping of pyrolysis furnaces for cracking hydrocarbon residues from processing of petroleum (RHC), such as primary vacuum residues, vacuum residues from hydrogenation cracking, non-converted oil residues from hydrogenation cracking, various distillation layers of primary vacuum distillates, distillates from hydrogenation cracking, non-converted fractions from fluid catalytic cracking during processing of petroleum, is one of the main problems of thermal cracking, because it can cause operation failures. [0003] Hydrogenation cracking of hydrocarbon residues from the vacuum distillation is performed in order to increase yield from hydrocarbon raw material through obtaining further amounts of lighter fractions from the fractions, which otherwise would be disposed. [0004] These raw materials are characterized by the high carbon/hydrogen ratio, the high ratio of aromatic compounds and compounds with double bonds, which tend to polymerize and form coke at elevated temperature. This composition of hydrocarbon residues presents high value of carbon determined according to Conradson, and high content of compounds insoluble in n-heptane, mainly asphaltenes.

[0005] Formation of asphaltenic deposits in the furnace piping precedes formation of coke. The formation of coke starts with precipitation of asphaltenic compounds as a consequence of disturbing the equilibrium between asphaltenes and resins what in turn disturbs the equilibrium of the whole original colloid system. Colloid system of hydrocarbon residues consists of micelles, which cores consist of asphaltenes, on which the resins are absorbed.

[0006] The external shell of a micelle consists of hydrocarbon molecules. If the concentration of resins is sufficient, asphaltenes are peptized and they do not come out from the system. If the concentration of resins on the surface of micelles is low, they mutually interact and they form a network, gel-like structure. With further increase of concentration of asphaltenes, or after addition of a hydrocarbon, asphaltenes coagulate and precipitate.

[0007] At elevated temperature condensation and polymerization reactions between present compounds occur, a metastable meso-form is formed, and consequently, with the heat, coke is created out of it. However, this mechanism is not the only way of coke formation. To its formation also contributes the transfer of carbenium ions initiated by protons, predominantly in the reaction section of hydrocarbon cracking of hydrocarbon residues itself, which results in high condensed hydrocarbons with high carbon/hydrogen ratio, and consequently, with high temperature, leads to coke formation. [0008] Coke deposits restrict heat transfer through piping walls of the hydrogenation cracking plant, resulting in their insufficient cooling by raw material, and local overheating with possible consequent burning of the piping. [0009] Additives for the mentioned use are required to have detergent and stabilizing influence on the colloid system of micelles with asphaltenic cores, and if possible, simultaneously also the ability to block the transfer of carbenium ions. Highly effective additives posses both properties at once. Effective compounds are for example compounds of alkylsulfonic acids type, some aminophenols and N-alkylamine compounds, which has primarily detergent effect, or some naphthene acids and their salts, especially molybdenum and cobalt salts, which block the transfer of carbenium cation. [0010] As coke formation inhibitors in petrochemical processes were patented for example compounds based on succinimide derivates ( EP 0632121 (KURITA WATER IND LTD [JP]) 04.01.1995 ), compounds based on quaternary ammonium salts ( EP 0978574 (NALCO CHEMICALS CO [US]) 09.02.2000 ), or compounds derived from acrylonitrile acid ( EP 0872475 (NALCO EXXON ENERGY CHEM LP [US]) 05.05.1998 ). Other patent documents describe compounds as for example polyalkenyl tiophosphone acid ( EP 0326729 (BETZ EUROP INC [US]) 09.08.1989 ), various types of oximes, hydrazines and carbohydrazines ( WO 9213929 (ASCHEM I P INC [US]) 25.05.1993 ). [0011] Additives currently used in processes of hydrogenation cracking of hydrocarbon residues have primarily detergent effect and are not able to block precursors of coke formation. They are also used in processes of product separation, and for storage after the hydrogenation cracking. However, additives are also required not to influence qualitative properties of gasolines and medium distillates. Disclosure of the Invention [0012] Subject of the present invention are substituted polyethylene polyamines, method of their preparation and their use as additives inhibiting or limiting the formation of deposits in the process of hydrocarbon residues cracking, which simultaneously prevent creation of coke precursors, being especially asphaltenes, and which absorb free radicals affecting mainly stability of products in during their separation and storage. Compounds, which are subject of this invention, due to their ability to inhibit transfer of carbenium ion, affect also cracking of the hydrocarbon residues in the reaction section. They do not influence the activity of catalysts used in the cracking process and thus they do not affect yield of the process. As high-boiling compounds they are not cracked in the reaction section, they cumulate in the residue of vacuum distillation, where, basically, coke is formed most frequently, whereas reducing the possibility of fouling the vacuum distillation apparatus. For the same reason, additives can anyhow affect neither the quality of gasolines nor the medium distillate fractions. [0013] The additives are soluble in aromatic solvents as for example xylene, toluene, benzene, and in strong polar organic solvents as methanol, ethanol, butanol, cyclohexanol, in polyvalent alcohols as for example glycol, propylene glycol and other polyvalent alcohols, further in chlorohydrocarbons as for example chlorofom, tetrachlormethane, trichlorethylene etc. [0014] The additives are added to the raw material for hydrogenation cracking of hydrocarbon residues, with advantage in the form of a solution of the additive in aromatic solvent. Optimal effective concentration ranges from 10 to 1500 ppm. It is desired the additive concentrations to be as low as possible. [0015] Effectiveness of the additives can be tested using the following methods: 1. Test with membrane filter - medium distillate with the additive under thermal stress is compared with a sample of medium distillate without the additive. After the test, samples are filtered through membrane filter and a color change of the filtrate and the amount of sediments on the filter compared. 2. Sedimentation test (accelerated) - a sample of medium distillate with the additive and without the additive are thermally stressed in given time interval, and simultaneously oxidized by air stream. At the end of the time interval samples are filtered and a color change of the filtrate and the amount of sediments on the filter compared. 3. Hot test (thermal test) - samples of medium distillate with the additive and without the additive are thermally stressed in given time interval. At the end of the time interval color numbers according to Robinson or according to ASTM are compared. 4. Filtration test - after the hot test samples are filtered and weight difference of sediments on the filter is compared. 5. Measuring the stability using Fl index - sample of the medium distillate with the additive and without the additive is dissolved in aromatic solvent and with titration by n-alkaline compound the changes of refraction index are titrated. At the point of instability in the significant change of refraction index, Fl index is determined from the volume of the aromatic solvent and of the titration reagent.

[0016] According to this invention, compounds effective as antifouling additives are in general linear alkyl- or aryl- substituted polyethylene polyamines having general formula (I):

where: Rι, R2, R3, R = H alkyls with one to 50 atoms of carbon X1 , X2, X3, X4 = O to 20 a, b, c = 0 or 1 [0017] Compounds of this type with identified inhibiting or restricting influence on coke formation in pyrolysis furnaces for cracking of hydrocarbon residues are prepared by poly-condensation of linear polyethylene polyamines with formaldehyde or by multistage reaction of linear polyethylene polyamines with properly selected number of ethylenamine - mers -(CH2-CH2-NH)- with formaldehyde and phenol, which can be further substituted on benzene core by reaction with formaldehyde and alkylamines having suitable length of ending alkylsubstitutes Rι, R2, R3, R4. Instead of phenol it is possible to use phenols, which are substituted in meta or para position, so that the orto position on the benzene core is not deactivated. In this regard suitable substituents are alkyl-, aryl-, aminoaryl, nitro-group, heterocyclic compound or amide. Instead of phenol 1-naphtol and its similar arylalcohols can be used.

[0018] Structure of the additives according to present invention is mainly defined by: 1. the type of used polyethylene polyamine i.e. the number of -mers - (CH2-CH2-NH)-, by the type of substitution of end groups of polyethylene polyamine, and by the number of carbons in alkylsubstituent, 2. the molar ratio of polyethylene polyamine to formaldehyde used in the reaction, 3. the number of stages of the poly-condensation reaction of polyethylene polyamines with formaldehyde, 4. the number of subsequent stages of the poly-condensation reactions of the product of polycondensation of polyethylene polyamine, in the first, respectively in the second stage of reaction with phenol and formaldehyde. [0019] The most suitable solvent for synthesis and application of the additives is xylene. Instead of xylene another aromatic solvents can also be used, e.g. benzene, tholuene, mezitylene, and the medium distillates e.g. kerosene or gas oil, heavy gasoline or pyrolysis gasoline. [0020] Compounds having general structural formula (I), of which some typical compounds are presented in the examples 1 to 5 of modes for carrying out the invention, can be used according to present invention as additives individually, or as mixtures of selected compounds, for the process of cracking of residues, in such an amount, that the sum of concentrations of the additives in the raw mixture for cracking of hydrocarbon residues from oil processing is in the range from 10 to 1000 ppm. Individual additives or their mixtures in mentioned solvents are continuously added to streams of raw materials, streams of intermediate products, and products from hydrogenation cracking of residues. [0021] The sum of concentrations of active compounds in the concentrates of additives can vary from 1 to 95 % by weight. In compliance with the operational needs, compounds having general structural formula (I) can be used as additives to raw materials, and product streams of the operated technological devices as well as to stored products and intermediate products. Mode(s) for carrying out the invention [0022] Following modes for carrying out the invention present methods of preparation of the exemplary types of compounds having general structural formula (I), usable as additives inhibiting or limiting formation of resins and coke in the equipment for thermal cracking of hydrocarbon residues, such as primary vacuum residues, vacuum residues from hydrogenation cracking, non-converted oil from hydrogenation cracking, as well various distillation layers of primary vacuum distillates and distillates from hydrogenation cracking, and non-converted fractions from the fluid catalytic cracking during processing of petroleum, and method of their use. Present examples are not in any sense limiting for the scope of patent claims.

Example 1

[0023] Amounts of 250g of xylene, 25.8g of diethylene triamine and 134g of octadecylamine are charged to 5-liter reactor with stirrer, reverse cooler and temperature regulation. To the mixture, 40 g of 37% water solution of formaldehyde is gradually added at such a rate that the mixture temperature does not exceed 30°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature within 30 to 35°C for 2 hours.

2 CH^-CH^r-_NH₂ + Yψ— CH_j-CHj-NH— CH^-CHj-NHg + 2 HCHO »^►

CH^CH₂-^_ H- CH₂

[0024] Reaction water is removed by azeotropic distillation. Distillation is finished when pure xylene without water starts to distill. The product is suitable for use as inhibiting additive. Example 2 [0025] Amounts of 250g of xylene, 94g of phenol and 52g of diethylene triamine are charged to 5-liter reactor with stirrer, reverse cooler and temperature regulation. To the mixture, 83 g of 37% water solution of formaldehyde is gradually added at such a rate that the mixture temperature does not exceed 35°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the above temperature for 2 hours. + H ι₂. — CH_j— CH₂— H— CH2- CH2~NH₂ + 2 HCHO

[0026] Reaction water is removed by azeotropic distillation. Distillation is finished when pure xylene without water starts to distill. The product is suitable for use as inhibiting additive.

Example 3

[0027] Amounts of 600g of xylene, 94g of phenol and 111 g of diethylene triamine are charged to 5-liter reactor with stirrer, reverse cooler and temperature regulation. Mixture is heated to 35°C and 80g of 37% water solution of formaldehyde is gradually added at such a rate that the mixture temperature does not exceed 40"C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature within 35 to 40°C for 2 hours.

[0028] Reaction water is removed by azeotropic distillation. Distillation is finished when pure xylene without water starts to distill. The product is used as input for the second stage of the reaction.

+ H₂N— CH 2" CH₂— NH— CH2- CH₂— NH₂ + 2 HCHO

[0029] To the product obtained from the first stage, 269g of octadecylamine is dosed, and 80g of 37 % water solution of formaldehyde is gradually added to the mixture in such a rate that the mixture temperature does not exceed 40°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature 40°C for 2 hours. Distillation is finished when pure xylene without water starts to distill. The product is suitable for use as inhibiting additive.

Example 4

[0030] Amounts of 600g of xylene, 94g of phenol and 51 g of diethylene triamine are charged to 5-liter reactor with stirrer, reverse cooler and temperature regulation. To the mixture, at the temperature 35°C, 162g of 37% water solution of formaldehyde is dosed at such a rate that the mixture temperature does not exceed 38°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature within 35 to 40°C for 2 hours. Reaction water is removed by azeotropic distillation. Distillation is finished when pure xylene without water starts to distill. The product is used as input for the second stage of the reaction. [0031] To the product obtained from the first stage, 269g of octadecylamine is dosed, and 162g of 37 % water solution of formaldehyde is gradually added to the mixture in such a rate that the mixture temperature does not exceed 40°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature 40°C for 2 hours. Distillation is finished when pure xylene without water starts to distill. The product is used as input for the third stage of the reaction.

OH (Q) ⁺ H₂N— CH2- CH₂— NH— CH2— CH2- NH₂ + 2 HCHO

+ H, N— CH— CH₂— NH— CH2-CH₂— NH₂ H₂O + 2 HCHO

[0032] To the product from the second stage, 3g of zeolite of Y type with 4-12 module and 26g of diethylene triamine are addedin the third stage of the reaction. To the mixture 81 g of 37 % water solution of formaldehyde is gradually added in such a rate that the mixture temperature does not exceed 40°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature within 40 to 45°C for 2 hours. Reaction water is removed by azeotropic distillation. Distillation is finished when pure xylene without water starts to distill. The product is suitable for use as inhibiting additive.

Example 5

[0033] Amounts of 600g of xylene, 94g of phenol and 51 g of diethylene triamine are charged to 5-liter reactor with stirrer, reverse cooler and temperature regulation. To the mixture, at the temperature 35°C, 162g of 37 % water solution of formaldehyde is gradually added at such a rate that the mixture temperature does not exceed 38°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature within 35 to 40°C for 2 hours. Reaction water is removed by azeotropic distillation. Distillation is finished when pure xylene without water starts to distill. The product is used as input for the second stage of the reaction.

[0034] To the product obtained in the first stage, 269g of octadecylamine is dosed, and 162g of 37 % water solution of formaldehyde is gradually added to the mixture in such a rate that the mixture temperature does not exceed 40°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature 40°C for 2 hours. Reaction water is removed by azeotropic distillation. Distillation is finished when pure xylene without water starts to distill. The product is used as input for the third stage of the reaction. [0035] To the product from the second stage 3g of acidific alumina and 52g of diethylene triamine are added. To the mixture 162g of 37% water solution of formaldehyde is gradually added in such a rate that the mixture temperature does not exceed 50°C. After adding the formaldehyde, reaction mixture, continuously stirred, is retained at the temperature 50°C for 2 hours. Reaction water is removed by azeotropic distillation. Distillation is finished when pure xylene without water starts to distill. The product is suitable for use as inhibiting additive.

OH 2 (Q) ⁺ H₂ — CH_j- CH₂— NH— CH^ CH_j- NH- + 2 HCHO

+2 H₂ N— CH_j-CH₂— NH— CH_j— CH₂— NH₂ -2Hp + 2 HCHO

H₂ N -(CHj-CH_∑- NH^-HsC

Industrial applicability

[0036] Present invention is industrially applicable in synthesis and use of compounds effective as additives inhibiting, or limiting the formation of coke, or resins in equipment for thermal cracking of hydrocarbon residues, such as vacuum residues, vacuum residues from the processes of hydrogenation cracking, non-converted oils from the process of hydrogenation cracking, and various distillation layers of primary vacuum distillates and distillates from the process of hydrogenation cracking and non-converted fractions from the process of fluid catalytic cracking from processing of petroleum.

Claims

1. 1. Substituted polyethylene polyamines having general formula:

where Rι,R2, R3, R₄ = H or alkyls with one to fifty carbon atoms X1 , X2, X3, X4 = 0 to 20 a, b, c = 0 or 1

2. Method of preparation of substituted polyethylene polyamines according to claim 1 , characterized in that, one mole of at least one linear polyethylene polyamine having general formula (CH2-CH2)n(NH)_n+ι, where n = 1 - 50 is brought to reaction with one mole of at least one alkylamine having general formula R-NH2, where R is alkyl with 1 to 50 atoms of carbon, and with two moles of formaldehyde in a solvent, in the time interval of at least 120 minutes and at the temperature from 30 to 50 °C.

3. Method of preparation of substituted polyethylene polyamines according to claim 1 , characterized in that, one mole of at least one linear polyamine having general formula (CH2-CH2)n(NH)_n+ι, where n = 1-50 is brought to reaction with two moles of formaldehyde in a solvent in the time interval of at least 120 minutes and at the temperature from 30 to 50 °C.

4. Method of preparation of substituted polyethylene polyamines according to claim 1 , characterized in that, one mole of at least one linear polyamine having general formula (CH2-CH2)n(NH)_n+ι, where n = 1-50 is brought to reaction with two moles of alkylamine having general formula R-NH2, where R is alkyl with 1 to 50 atoms of carbon and with two moles of phenol in a solvent, and the product is brought to reaction in a solvent with four moles of formaldehyde in the time interval of at least 120 minutes and at the temperature from 30 to 50 °c.

5. Method of preparation of substituted polyethylenpolyamines according to claim 1, characterized in that, one mole of at least one linear polyamine having general formula (CH₂-CH₂)n(NH)nι-ι, where n = 1-50 is brought to reaction with two moles of alkylamine having general formula R-NH2, where R is alkyl with 1 to 50 atoms of carbon, two moles of phenol and two moles of formaldehyde i a solvent, in the time interval of at least 120 minutes and at the temperature from 30 to 50 "C and the product is in the second stage brought to reaction with two moles of alkylamine having general formula R-NH2 where R is alkyl with 1 to 50 atoms of carbon, with two moles of formaldehyde and then the product obtained is in the third stage brought to reaction with one mole of polyethylene polyamine having general formula (CH_-CH₂)n(NH)n*ι.

6. Method of preparation of substituted polyethylene polyamines according to claim 1 , characterized in that, one mole of at least one linear polyamine having general formula (CH₂-CH2)r,(NH)_π+ι. where π = 1-50 is brought fc eaction with two moles of phenol, and the product is brought to reaction with two moles of formaldehyde in a solvent in the time interval of at least 120 minutes and at the temperature from 30 to 50 °C, and then the product obtained is in the third stage brought to reaction with two moles of linear polyethylene polyamine having general formula (CH_-CH₂)n(NH)n₊ι.

7. Method of preparation of substituted polyethylenepolyamines according to claims 1 to 6, characterized in that, the suitable solvent for the preparation of substituted polyethylene polyamines is at least one substance selected from - group of substances: benzene, toluene, xylene, mezitylene, middle distilate, kerosene, gas oil, heavy gasoline, pyrolytic gasoline.

8. Use of substituted polyethylenepolyamines according to any of the claims 1 to 7 as inhibitor of formation of resins and coke in piping of pyrolysis furnaces characterized in that, at least one compound of substituted polyethylene polyamines in a solvent is dosed to streams of raw materials, or to streams of intermediate products, or to streams of products of cracking of hydrocarbon resides, whereas the sum of concentrations of components in solutions of substituted polyethylene polyamines is from 1 to 95 % by weight and overall concentration of substituted polyethylene polyamines in the steams of raw materials, or the streams of intermediate products is within 10 to 1000 ppm.

9. Use of substituted polyethylene polyamines according to claim 8, characterized in that, the suitable solvent for thinning of substituted polyethylene polyamines is at least one compound selected from group of compounds: methanol, ethanol, butanol, cyclohexanol, glycol, higher polyvalent alcohols, chloroform, tetrachlormethane, trichlorethylene.