阅读说明：本技术 一种催化裂化油浆阻垢剂及其制备方法 (Catalytic cracking slurry oil scale inhibitor and preparation method thereof ) 是由 顾吉 吴伟卫 顾富良 杨丽萍 于 2021-10-09 设计创作，主要内容包括：本发明公开了一种催化裂化油浆阻垢剂,它是以聚异丁烯丁二酰亚胺、硫磷化聚异丁烯钡盐、2,6-二叔丁基对甲酚和溶剂为原料；所述的异丁烯丁二酰亚胺、2,6-二叔丁基对甲酚和溶剂的质量比为(2～3):1:(5～6),所述的硫磷化聚异丁烯钡盐的用量为原料总量的2～10％；所述的溶剂为200#溶剂油和柴油质量比1.5:1～1:1的混合溶剂。本发明催化裂化油浆阻垢剂适用于掺炼渣油比例较高的催化裂化装置中油浆系统的阻垢和除垢,通常添加120～200ppm油浆阻垢剂即可达到90％以上的阻垢率。(The invention discloses a catalytic cracking slurry oil scale inhibitor, which takes polyisobutylene succinimide, sulfur-phosphorus polyisobutylene barium salt, 2, 6-di-tert-butyl-p-cresol and a solvent as raw materials; the mass ratio of the isobutylene succinimide to the 2, 6-di-tert-butyl-p-cresol to the solvent is (2-3) to 1 (5-6), and the using amount of the sulfur-phosphorus polyisobutene barium salt is 2-10% of the total amount of the raw materials; the solvent is a mixed solvent of 200# solvent oil and diesel oil in a mass ratio of 1.5: 1-1: 1. The catalytic cracking slurry oil scale inhibitor is suitable for scale inhibition and scale removal of a slurry oil system in a catalytic cracking device with high blending ratio of residual oil, and the scale inhibition rate can reach more than 90% by adding 120-200ppm of the slurry oil scale inhibitor.)

1. A catalytic cracking slurry oil scale inhibitor is characterized in that: the method takes polyisobutylene succinimide, sulfur-phosphorus polyisobutylene barium salt, 2, 6-di-tert-butyl-p-cresol and a solvent as raw materials; the mass ratio of the isobutylene succinimide to the 2, 6-di-tert-butyl-p-cresol to the solvent is (2-3) to 1 (5-6), and the amount of the barium salt of the sulfur-phosphorus polyisobutylene is 2-10% of the total amount of the raw materials.

2. The catalytic cracking slurry oil scale inhibitor according to claim 1, characterized in that: the mass ratio of the isobutylene succinimide to the 2, 6-di-tert-butyl-p-cresol to the solvent is (2-2.2) to 1 (5.8-6).

3. The catalytic cracking slurry oil scale inhibitor according to claim 1, characterized in that: the amount of the sulfur-phosphorus polyisobutene barium salt is 2-5% of the total amount of the raw materials.

4. The catalytic cracking slurry oil scale inhibitor according to claim 1, characterized in that: the solvent is a mixed solvent of 200# solvent oil and diesel oil in a mass ratio of 1.5: 1-1: 1.

5. The preparation method of the catalytic cracking slurry oil scale inhibitor of claim 1, which is characterized by comprising the following steps: the method comprises the following steps: adding barium sulfophosphorized polyisobutene salt and 2, 6-di-tert-butyl-p-cresol into a solvent while stirring at the temperature of 40-50 ℃, adding polyisobutene succinimide after complete dissolution, and stirring until dissolution to obtain the catalytic cracking slurry oil scale inhibitor.

Technical Field

The invention relates to a catalytic cracking slurry oil scale inhibitor and a preparation method thereof.

Background

Catalytic cracking units are one of the important units in refineries. After the oil gas after catalytic cracking reaction contains a large amount of catalyst fine powder, the catalyst fine powder still remains at the bottom of the fractionating tower or is circulated to a heat exchanger along with the oil slurry for deposition after the oil gas is washed by the oil slurry at the bottom of the fractionating tower, and the analysis result of ash elements shows that the catalyst powder in the scale deposit is about more than 60 percent, so the catalyst powder is an important cause of the scale deposit of a catalytic cracking oil slurry system. In addition, some inorganic scale deposits are corrosive substances or salts generated during the storage, transportation and refining of catalytic cracking raw materials. These small particle impurities can agglomerate into larger particles and when the particle deposition rate is greater than the system flow rate, the impurity particles are deposited back down.

With the continuous progress of catalytic cracking technology and the improvement of petroleum processing depth, the proportion of blended residual oil is continuously increased, and the catalytic cracking raw materials become more complex and heavier. Due to the deterioration of the properties of the raw oil, during the processing, substances such as polycyclic aromatic hydrocarbon, colloid, asphaltene and the like rich in the oil slurry are subjected to dehydrogenation condensation reaction under the catalytic action of transition metal in the oil slurry to generate a precursor of coke, and the precursor is adhered to the surface of equipment. The organic polymer can accelerate the aggregation of inorganic particles such as catalyst and the like, and the inorganic particles are deposited in an oil slurry system, so that the problem of scaling and blockage of the oil slurry system is serious day by day: the slurry oil system is mainly easy to form scale between tube bundles of the raw material heat exchanger, the heat exchange effect is influenced, and the heat exchanger is blocked in serious cases. Coking is easy to occur in the heating furnace tube and the reactor. Thereby forcing down production and even unplanned shutdowns. Therefore, solving the problems of coking and fouling of the catalytic cracking slurry system has become an important issue for ensuring the long-term operation of the catalytic cracking unit.

Disclosure of Invention

The invention aims to provide a catalytic cracking slurry oil scale inhibitor aiming at the problems of coking and fouling of a catalytic cracking slurry oil system.

The purpose of the invention is realized by the following technical scheme:

a catalytic cracking slurry oil antisludging agent, which takes polyisobutylene succinimide, sulfur-phosphorus polyisobutylene barium salt, 2, 6-di-tert-butyl-p-cresol and solvent as raw materials; the mass ratio of the isobutylene succinimide to the 2, 6-di-tert-butyl-p-cresol to the solvent is (2-3) to 1 (5-6), and the amount of the barium sulfophosphatized polyisobutylene salt is 2-10 wt% of the total amount of the raw materials.

Preferably, the mass ratio of the isobutylene succinimide to the 2, 6-di-tert-butyl-p-cresol to the solvent is (2-2.2) to 1 (5.8-6).

Preferably, the amount of the sulfur-phosphorus polyisobutene barium salt is 2-5 wt% of the total amount of the raw materials.

The solvent is a mixed solvent of 200# solvent oil and diesel oil in a mass ratio of 1.5: 1-1: 1.

The diesel oil is light diesel oil, and particularly 0# light diesel oil can be selected.

The invention also aims to provide a preparation method of the catalytic cracking slurry oil scale inhibitor, which comprises the following steps: adding barium sulfophosphorized polyisobutene salt and 2, 6-di-tert-butyl-p-cresol into a solvent while stirring at the temperature of 40-50 ℃, adding polyisobutene succinimide after complete dissolution, and stirring until dissolution to obtain the catalytic cracking slurry oil scale inhibitor. The different charging sequences have certain influence on the service performance of the scale inhibitor, the catalytic cracking slurry oil scale inhibitor is prepared according to the charging sequence of the invention, and the viscosity is minimum after the catalytic cracking slurry oil scale inhibitor is added into the slurry oil, which indicates that the scale inhibitor prepared by the charging sequence has the best performance.

The catalytic cracking slurry oil scale inhibitor is a multifunctional composite additive which is developed aiming at the scaling mechanism of slurry oil raw materials and does not contain metal ions, can effectively inhibit free radical polymerization reaction initiated by S, N, O in the raw materials, can react with the metal ions in the slurry oil to form a stable complex, and avoids the formation of scale caused by metal ions such as iron, copper and the like; the insoluble suspended substances such as catalyst powder, corrosion products, salt and the like contained in the oil slurry raw material can be dispersed so as to limit the particles from increasing to deposit and scale; the protective film can be formed on the surfaces of equipment and pipelines, and can simultaneously neutralize acidic substances in slurry oil raw materials, so that the acidic substances are not corroded by the acidic substances in oil products, the corrosion of the equipment is inhibited, the inner surfaces of the equipment and the pipelines are kept smooth, the service life of the equipment and the pipelines of a hydrocarbon oil system is prolonged, the heat transfer efficiency of a heat exchanger is improved, and the energy consumption of the device is reduced. The weight of the coke-forming board of the sulfur-phosphorus polyisobutylene barium salt is increased by less than that of other detergents such as high-base-number synthetic calcium sulfonate T106, super-base-number synthetic magnesium sulfonate T107 and the like, the high-temperature detergency is good, the neutralization capacity is strong, the antirust property is good, and the dispersant has certain dispersibility, and the isobutene succinimide synergistically limits the particle enlargement, deposition and scaling in the slurry raw material. The 2, 6-di-tert-butyl-p-cresol can reduce the glue quality generated by autoxidation in the oil slurry and delay oxidation.

The catalytic cracking slurry oil scale inhibitor has strong oxidation resistance and good thermal stability, and can be used at a higher temperature of about 500 ℃ without influencing the property and the service performance of the catalytic cracking slurry oil scale inhibitor.

The invention relates to a method for using a catalytic cracking oil slurry antisludging agent, which is characterized in that the oil slurry antisludging agent is added to an inlet of a raw material oil pump of an oil slurry device or the position before raw material oil enters a heat exchanger by a metering pump, and the antisludging agent passes through the raw material heat exchanger along with the raw material and then enters a reactor. The adding amount of the scale inhibitor is 120-200 ppm. The catalytic cracking slurry oil scale inhibitor is suitable for scale inhibition and scale removal of a slurry oil system in a catalytic cracking device with high blending ratio of residual oil, and the scale inhibition rate can reach more than 90% by adding 120-200ppm of the slurry oil scale inhibitor.

Drawings

FIG. 1 is a laboratory evaluation device for scale inhibitor performance.

In the figure, 1-stock tank; 2-a micro-metering pump; 3-raw material inlet temperature controller; 4-testing the outer wall temperature controller of the tube; 5, heating a furnace; 6-test tube; 7-a receiving slot; 8-raw material outlet temperature recorder.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

Example 1

A catalytic cracking slurry oil scale inhibitor takes polyisobutylene succinimide, sulfur-phosphorus polyisobutylene barium salt, 2, 6-di-tert-butyl-p-cresol, No. 0 light diesel oil and 200# solvent oil as raw materials, wherein the mass ratio of the polyisobutylene succinimide, the 2, 6-di-tert-butyl-p-cresol, the No. 0 light diesel oil and the 200# solvent oil is 24:11:30:35, and the amount of the sulfur-phosphorus polyisobutylene barium salt accounts for 2 wt% of the total amount of the raw materials.

The catalytic cracking slurry oil scale inhibitor is prepared by the following method: placing No. 0 light diesel oil and No. 200 solvent oil into a reactor, starting stirring, heating to 40 ℃, adding sulfur-phosphorus polyisobutene barium salt and 2, 6-di-tert-butyl-p-cresol, after completely dissolving, adding polyisobutene succinimide, and stirring until dissolving to obtain the catalytic cracking slurry oil scale inhibitor.

TABLE 1 Main indexes of the catalytic cracking slurry scale inhibitor of the example

Appearance of the producta	Brownish red uniform liquid
		Oil solubilityb	Without phase separation
Flash point (closed mouth), deg.C	61
		Freezing point, deg.C	-20
Water content%	1.00

Note: a: and (3) injecting 25-30 mL of sample into a clean, dry and transparent 50mL colorimetric tube, standing for 10min at room temperature, and directly performing visual inspection under the transmission of sunlight or a fluorescent lamp.

b: five clean, dry and transparent 50mL colorimetric tubes are taken and numbered in sequence. Adding 15mL, 5mL, 15mL and 25mL samples into the five colorimetric tubes respectively, adding 15mL, 25mL, 5mL and 5mL straight-run diesel oil into the colorimetric tubes with corresponding numbers in sequence, shaking up, standing for 8 hours at room temperature, and directly visually observing under the transmission of sunlight or a fluorescent lamp.

As can be seen from Table 1, the catalytic cracking slurry oil scale inhibitor of the present embodiment has good intersolubility, can be mixed with liquid hydrocarbons such as aromatic hydrocarbons, alkanes and the like in any proportion, has low freezing point, low viscosity and convenient use.

The scale inhibition performance of the catalytic cracking slurry scale inhibitor of the embodiment was examined by adopting Cangzhou oil refinery slurry and according to the laboratory evaluation device for scale inhibitor performance shown in FIG. 1, the dosage of the slurry scale inhibitor was 40-200ppm, the slurry flow rate was 200mL/h, the inlet temperature was 100 ℃ and the furnace temperature was 500 ℃.

TABLE 2 Effect of oil slurry antisludging agent dosage on antisludging rate

As can be seen from Table 2, the scale inhibition rate increases with the increase of the addition amount, but the scale inhibition rate does not increase obviously any more and tends to be stable when the addition amount is a certain amount, and the scale inhibition rate is more than or equal to 90 percent when the addition amount of the oil slurry scale inhibitor is 120-200ppm (mu g/g), so that the scale inhibition effect is good. It is stated that the more the addition of the scale inhibitor is not preferable, the reasonable addition amount is provided, and the suitable addition amount is 100-200 ppm.

Example 2

A catalytic cracking slurry oil scale inhibitor takes polyisobutylene succinimide, sulfur-phosphorus polyisobutylene barium salt, 2, 6-di-tert-butyl-p-cresol, No. 0 light diesel oil and 200# solvent oil as raw materials, wherein the mass ratio of the polyisobutylene succinimide, the 2, 6-di-tert-butyl-p-cresol, the No. 0 light diesel oil and the 200# solvent oil is 24:11:30:35, and the amount of the sulfur-phosphorus polyisobutylene barium salt accounts for 3 wt% of the total amount of the raw materials.

The preparation method of the catalytic cracking slurry oil scale inhibitor in the embodiment is the same as that in the embodiment 1.

Example 3

A catalytic cracking slurry oil scale inhibitor takes polyisobutylene succinimide, sulfur-phosphorus polyisobutylene barium salt, 2, 6-di-tert-butyl-p-cresol, No. 0 light diesel oil and 200# solvent oil as raw materials, wherein the mass ratio of the polyisobutylene succinimide, the 2, 6-di-tert-butyl-p-cresol, the No. 0 light diesel oil and the 200# solvent oil is 24:11:30:35, and the amount of the sulfur-phosphorus polyisobutylene barium salt accounts for 5 wt% of the total amount of the raw materials.

The preparation method of the catalytic cracking slurry oil scale inhibitor in the embodiment is the same as that in the embodiment 1.