阅读说明：本技术 一种催化裂化油浆沉降剂 (Catalytic cracking slurry oil settling agent ) 是由 谢天明 刘鹏 颜梦秋 葛盛才 张佩祥 于 2021-09-27 设计创作，主要内容包括：本发明公开了一种催化裂化油浆沉降剂,其包括5-50wt％脂肪醇聚氧丙烯醚、5-40wt％脂肪醇嵌段聚醚改性物、0.5-20wt％聚丙烯酸酯和20-80wt％芳烃溶剂油A。本申请中的催化裂化油浆沉降剂生产工艺简单,油浆适用性广、使用条件弹性大、灰分脱除率高等优点。(The invention discloses a catalytic cracking slurry settling agent, which comprises 5-50 wt% of fatty alcohol polyoxypropylene ether, 5-40 wt% of fatty alcohol block polyether modifier, 0.5-20 wt% of polyacrylate and 20-80 wt% of aromatic solvent oil A. The catalytic cracking slurry oil settling agent has the advantages of simple production process, wide slurry oil applicability, large elasticity of use conditions, high ash removal rate and the like.)

1. A catalytic cracking slurry oil settling agent is characterized by comprising 5-50 wt% of fatty alcohol polyoxypropylene ether, 5-40 wt% of fatty alcohol block polyether modifier, 0.5-20 wt% of polyacrylate and 20-80 wt% of aromatic solvent oil A.

2. The catalytic cracking slurry settling agent of claim 1, comprising 5-40 wt% fatty alcohol polyoxypropylene ether, 5-30 wt% fatty alcohol block polyether modifier, 0.5-10 wt% polyacrylate, and 30-80 wt% aromatic solvent oil A.

3. Catalytic cracking slurry settling agent according to claim 1,

the fatty alcohol polyoxypropylene ether is 1, 2-propylene glycol polyoxypropylene ether, 1, 2-butylene glycol polyoxypropylene ether, 1, 2-pentanediol polyoxypropylene ether, glycerol polyoxypropylene ether or 1,2, 3-pentanetriol polyoxypropylene ether;

the fatty alcohol block polyether modifier is 1, 2-propylene glycol block polyether modifier, 1, 2-butanediol block polyether modifier, 1, 2-pentanediol block polyether modifier, glycerol block polyether modifier or 1,2, 3-pentanetriol block polyether modifier.

4. The catalytic cracking slurry settling agent of claim 1, wherein the polyacrylate is polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, or polypentyl acrylate.

5. The catalytic cracking slurry settling agent of claim 1, wherein the fatty alcohol block polyether modifier is prepared by the following method: adding fatty alcohol block polyether, aromatic hydrocarbon solvent oil B, organic acid and diisocyanate into a reactor, and stirring and reacting for 1-24h at 30-150 ℃ to obtain the fatty alcohol block polyether modifier.

6. The catalytic cracking slurry oil settling agent of claim 5, wherein the fatty alcohol polyoxypropylene ether has a number average molecular weight of 2000-; the number average molecular weight of the fatty alcohol block polyether is 1000-20000; the number average molecular weight of the polyacrylate is 10000-1000000.

7. The catalytic cracking slurry settling agent of claim 5, wherein aromatic mineral spirit A and aromatic mineral spirit B are 1000# aromatic mineral spirit, 1500# aromatic mineral spirit, 1800# aromatic mineral spirit or 2000# aromatic mineral spirit.

8. The catalytic cracking slurry settling agent of claim 5, wherein the organic acid is formic acid, acetic acid, oxalic acid, benzoic acid, or phenylacetic acid.

9. The catalytic cracking slurry settling agent of claim 5, wherein the diisocyanate is toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate.

10. The catalytic cracking slurry settling agent of claim 5, wherein the mass ratio of the fatty alcohol block polyether, the aromatic hydrocarbon solvent oil B, the organic acid and the diisocyanate is 100 (40-200): (0.01-5): 0.2-10).

Technical Field

The invention relates to a catalytic cracking slurry oil settling agent.

Background

The catalytic cracking slurry oil contains about 50% of saturated hydrocarbon, 40% of aromatic hydrocarbon and polycyclic aromatic hydrocarbon, and 10% of colloid and asphaltene, and can exert huge economic benefit if the colloid and the asphaltene are effectively separated and deeply processed. However, the catalytic cracking slurry oil contains catalyst damaged particles with the different contents of 2000-50000ppm, which severely limits further deep processing and value-added utilization. If the effective separation of catalyst fine particles in the catalytic cracking slurry oil can be realized, the components of the poor quality slurry oil can be allocated to other fields such as high-value new standard ship fuel, coking process, heavy chemical products and the like in the largest proportion, and the comprehensive promotion of economic benefit, environmental protection and safety is realized.

The effective removal of catalyst fines from a catalytically cracked slurry oil is summarized as follows: high temperature centrifugal separation technology, high temperature filtration method, electrostatic separation method, natural sedimentation method, sedimentation agent sedimentation centrifugal separation method. The sedimentation method of the sedimentation agent has the advantages of simple equipment, simple and convenient operation and low operation cost, and is the most widely used method in the industry at present.

Because the sources of crude oil used in various refineries are different, a certain amount of atmospheric residue, coker gas oil and vacuum residue can be added in the catalytic cracking process, so that the composition and property difference of catalytic cracking oil slurry in various refineries is large, and the requirement on the applicability of the oil slurry settling agent is high, so that the oil slurry settling agent product of various companies in the market is difficult to popularize and apply in a large scale.

Disclosure of Invention

In order to solve the problems, the invention provides a catalytic cracking slurry oil settling agent which comprises 5-50 wt% of fatty alcohol polyoxypropylene ether, 5-40 wt% of fatty alcohol block polyether modifier, 0.5-20 wt% of polyacrylate and 20-80 wt% of aromatic hydrocarbon solvent oil A. Further preferably comprises 5-40 wt% of fatty alcohol polyoxypropylene ether, 5-30 wt% of fatty alcohol block polyether modifier, 0.5-10 wt% of polyacrylate and 30-80 wt% of aromatic solvent oil A.

The catalytic cracking slurry oil settling agent has the advantages of simple production process, wide slurry oil applicability, large elasticity of use conditions, high ash removal rate and the like. During preparation, the components are only required to be uniformly mixed, and special temperature and pressure are not required.

The inventor of the application finds in research that three functions of dissolution and dispersion, electric elimination and agglomeration and flocculation and sedimentation of the slurry oil sedimentation agent are the key points of catalytic cracking slurry oil ash removal. The Polyoxypropylene (PO) end in the fatty alcohol polyoxypropylene ether is a strong oil-soluble group, can be quickly dissolved and dispersed into an oil slurry system, and is beneficial to the penetration of the fatty alcohol block polyether modifier to the contact surface of the oil slurry and catalyst particles; the fatty alcohol block modifier and fatty alcohol polyoxypropylene ether form a synergistic effect, so that an electric double layer on the surface of catalyst particles is eliminated, and fine particle agglomeration is promoted; polyacrylate and particles form hydrogen bonds or ion pairs, and a bridging effect is formed under the action of van der Waals force, so that the flocculation and sedimentation of the particles are accelerated.

Specifically, the fatty alcohol polyoxypropylene ether is 1, 2-propylene glycol polyoxypropylene ether, 1, 2-butylene glycol polyoxypropylene ether, 1, 2-pentanediol polyoxypropylene ether, glycerol polyoxypropylene ether or 1,2, 3-pentanetriol polyoxypropylene ether;

the fatty alcohol block polyether modifier is 1, 2-propylene glycol block polyether modifier, 1, 2-butanediol block polyether modifier, 1, 2-pentanediol block polyether modifier, glycerol block polyether modifier or 1,2, 3-pentanetriol block polyether modifier. One end of the fatty alcohol polyoxypropylene ether is fatty alcohol, and the other end of the fatty alcohol polyoxypropylene ether is PO, wherein the PO end has strong oil solubility and can be quickly dissolved and dispersed into an oil slurry system; the fatty alcohol end has the same property with the fatty alcohol end in the fatty alcohol block polyether modifier, and the fatty alcohol block polyether modifier is favorable for penetrating into the contact surface of the oil slurry and the catalyst particles. And the special C ═ O bond and C-N bond in the fatty alcohol block polyether modifier can play a role in eliminating the electric double layer on the surface of the catalyst particles and promoting the agglomeration of fine particles.

Specifically, to ensure the sedimentation effect, the polyacrylate is polymethyl acrylate, polyethyl acrylate, polypropylene acrylate, polybutyl acrylate or polypentyl acrylate.

Specifically, fatty alcohol block polyether, aromatic hydrocarbon solvent oil B, organic acid and diisocyanate are added into a reactor and stirred to react for 1-24h at the temperature of 30-150 ℃ to obtain the fatty alcohol block polyether modifier. When the reaction temperature is too high, the molecular weight of reactants is too large to form colloid, and when the reaction temperature is too low, the reactants react too slowly; when the reaction time is too short, the molecular weight of the reactant is too low, and when the reaction time is too long, the reactant may form a colloid due to an excessively large molecular weight.

Preferably, the number average molecular weight of the fatty alcohol polyoxypropylene ether is 2000-; the number average molecular weight of the fatty alcohol block polyether is 1000-20000; the number average molecular weight of the polyacrylate is 10000-1000000. The higher the molecular weight of the fatty alcohol polyoxypropylene ether, the better the oil solubility, which is beneficial to the dispersion of the settling agent in the oil slurry; when the fatty alcohol block polyether is modified, the molecular weight can be increased by 2-10 times, and when the molecular weight is too high, the modification is easy to become colloid; polyacrylate action is flocculation sedimentation, so higher molecular weights need to be chosen.

Preferably, aromatic hydrocarbon solvent oil A and aromatic hydrocarbon solvent oil B are 1000# aromatic hydrocarbon solvent oil, 1500# aromatic hydrocarbon solvent oil, 1800# aromatic hydrocarbon solvent oil or 2000# aromatic hydrocarbon solvent oil. As the flash point of the aromatic hydrocarbon solvent oil No. 1000 is lower than 60 ℃, in order to enable the oil slurry settling agent product to be used as a class C substance, the aromatic hydrocarbon solvent oil A and the aromatic hydrocarbon solvent oil B are preferably 1500# aromatic hydrocarbon solvent oil, 1800# aromatic hydrocarbon solvent oil or 2000# aromatic hydrocarbon solvent oil.

Specifically, the organic acid is formic acid, acetic acid, oxalic acid, benzoic acid, or phenylacetic acid. The organic acid is preferably a commonly used short chain strong acid for catalyzing the reaction of the polyether with the diisocyanate.

Specifically, the diisocyanate is toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate. The common diisocyanate with benzene ring or cyclic group is preferred to enhance the oil solubility of the modified product.

Furthermore, the mass ratio of the fatty alcohol block polyether, the aromatic hydrocarbon solvent oil B, the organic acid and the diisocyanate is 100 (40-200): (0.01-5): 0.2-10). The feeding mass ratio of the reactants fully considers the modification degree of the polyether and the risk of gelling the reactants.

Detailed Description

The synthesis method of the fatty alcohol polyoxypropylene ether and the fatty alcohol block polyether is a common method, and the reaction method and conditions are not described in detail. The average molecular weights (number average molecular weights) of the fatty alcohol polyoxypropylene ether and the fatty alcohol block polyether were measured using an Agilent PL-GPC model 220 high temperature gel permeation chromatograph.

The performance evaluation method of the catalytic cracking slurry settling agent comprises the following steps:

1. preheating a catalytic cracking slurry oil sample at 110 ℃ for 4h, shaking up fully, taking 500ml, and injecting into a 500ml measuring cylinder with a plug.

2. 0.15-0.5ml of catalytic cracking slurry settling agent is added into a measuring cylinder with a plug.

3. And covering the measuring cylinder with a plug, and shaking the measuring cylinder back and forth 100 times while the measuring cylinder is hot so as to uniformly mix the catalytic cracking slurry settling agent and the catalytic cracking slurry.

4. And (3) placing the mixed graduated cylinder in a constant-temperature air blast oven, setting the temperature to be 80-120 ℃, and standing and settling for 24 hours or 48 hours.

5. Taking out the measuring cylinder with the plug from the constant-temperature air blast oven, keeping the measuring cylinder with the plug vertical, opening the plug, sucking catalytic cracking slurry oil (about 20-25g) at 100ml (20% height of the catalytic cracking slurry oil) of the measuring cylinder with the plug by using a 25ml pipette, putting the catalytic cracking slurry oil into a quartz cup to serve as a detection sample, and weighing to obtain the mass m of the detection sample₁。

6. Roasting the detection sample to constant weight by using an electric furnace and a muffle furnace in sequence, and weighing to obtain the ash mass m of the detection sample₂。

7. Taking 500ml of the catalytic cracking slurry oil sample which is preheated for 4 hours in the step 1 and fully shaken up, taking the 500ml of the catalytic cracking slurry oil sample as a basic sample, and weighing the basic sample to obtain the mass m of the basic sample₃Roasting the basic sample to constant weight by using an electric furnace and a muffle furnace in sequence, and weighing to obtain the ash mass m of the basic sample₄。

Ash removal rate of 1- (m)₂/m₁)/(m₄/m₃)。

Example 1

Adding 1, 2-propylene glycol block polyether with the number average molecular weight of 15000, 1500# solvent oil, formic acid and TDI (the mass ratio is 100:50:4:0.2) into a reactor, and stirring and reacting for 2h at 50 ℃ to obtain the 1, 2-propylene glycol block polyether modified substance.

Mixing 1, 2-propylene glycol polyoxypropylene ether, 1, 2-propylene glycol block polyether modifier, polymethyl acrylate and 1500# solvent oil according to the mass percentage of 10%, 40%, 1% and 49% to prepare the oil slurry settling agent.

Wherein the number average molecular weight of the 1, 2-propylene glycol polyoxypropylene ether is 3000, and the number average molecular weight of the polymethyl acrylate is 50000.

Example 2

Adding glycerol block polyether with the number average molecular weight of 2000, 2000# solvent oil, acetic acid and IPDI (the mass ratio is 100:150:1:8) into a reactor, and stirring and reacting for 12 hours at 120 ℃ to obtain the glycerol block polyether modified substance.

Mixing glycerol polyoxypropylene ether, glycerol block polyether modifier, polyethylacrylate and No. 2000 solvent oil according to the mass percent of 50%, 10% and 30% to obtain the oil slurry settling agent.

Wherein the number average molecular weight of glycerol polyoxypropylene ether is 60000, and the number average molecular weight of polyethylacrylate is 800000.

Example 3

Adding 1, 2-butanediol block polyether with the number average molecular weight of 6000, 1800# solvent oil, benzoic acid and MDI (mass ratio of 100:80:2:4) into a reactor, and stirring and reacting for 6 hours at 70 ℃ to obtain the 1, 2-butanediol block polyether modified substance.

Mixing 1, 2-butanediol polyoxypropylene ether, 1, 2-butanediol block polyether modifier, polypropylene acrylate and 1800# solvent oil according to the mass percent of 20%, 30%, 5% and 45% to obtain the oil slurry settling agent.

Wherein the number average molecular weight of the 1, 2-butanediol polyoxypropylene ether is 10000, and the number average molecular weight of the polypropylene acrylate is 200000.

Example 4

Adding 1,2, 3-pentanetriol block polyether with the number average molecular weight of 8000, 1800# solvent oil, formic acid and MDI (the mass ratio is 100:100:1:2) into a reactor, and stirring and reacting for 8 hours at 80 ℃ to obtain the 1,2, 3-pentanetriol block polyether modified substance.

Mixing 1,2, 3-pentanetriol polyoxypropylene ether, 1,2, 3-pentanetriol block polyether modifier, polybutyl acrylate and 1800# solvent oil according to the mass percentage of 10%, 40%, 1% and 49% to obtain the oil slurry settling agent.

Wherein the number average molecular weight of the 1,2, 3-pentanetriol polyoxypropylene ether is 5000, and the number average molecular weight of the polybutyl acrylate is 80000.

Example 5

Adding glycerol block polyether with the number average molecular weight of 8000, 1500# solvent oil, acetic acid and TDI (the mass ratio is 100:120:2:3) into a reactor, and stirring and reacting for 4 hours at 85 ℃ to obtain the glycerol block polyether modified substance.

Mixing glycerol polyoxypropylene ether, glycerol block polyether modifier, polymethyl acrylate and 1500# solvent oil according to the mass percent of 15%, 35%, 2% and 48% to obtain the oil slurry settling agent.

Wherein the number average molecular weight of the glycerol polyoxypropylene ether is 9000, and the number average molecular weight of the polymethyl acrylate is 200000.

And (3) comparing the performances of the slurry settling agent:

catalytic cracking external throwing slurry oil of medium petrochemical land-refining and famous petrochemical, medium petroleum Lanzhou petrochemical and Daqing refining are respectively taken as evaluation objects, a commercially available slurry oil settling agent EC3286A of Naerce (China) environmental protection technology service limited company, a commercially available slurry oil settling agent YS-4015 of Guangdong first new technology limited company and the slurry oil settling agent samples prepared in the examples 1-5 are selected for deashing performance comparison, and the results are shown in tables 1-4. As can be seen from tables 1-4, the slurry settling agent obtained in example 5 performed best as compared to examples 1-4; compared with the oil slurry settling agent prepared in the embodiment 1-4, the Naerceae EC3286A and the Yuexi YS-4015, the oil slurry settling agent prepared in the embodiment 5 has the most stable and optimal performance; after the performance evaluation of the slurry settling agent prepared in the examples 1-5 is settled for 48 hours, the ash removal rate of four catalytic cracking slurries exceeds 90%, while the removal rate of Naerce EC3286A is higher than 90% only when the famous petrochemical slurry is evaluated, and the removal rate of Yueji YS-4015 is higher than 90% only when the Daqing refined slurry is evaluated, so that the slurry settling agent prepared by the method has the widest applicability, and can meet the requirements of catalytic cracking slurries with different characteristics and use conditions (dosage and settling temperature).

Table 1 shows the results of evaluating the deliming performance of petrochemical, marine refining, catalytic cracking slurry oil

Table 2 shows the results of evaluating the deliming performance of petrochemical and famous petrochemical catalytic cracking slurry oil

Table 3 shows the results of evaluating the deliming performance of petroleum Lanzhou petrochemical catalytic cracking slurry oil

Table 4 shows the results of evaluating the deliming performance of the petroleum Daqing refining catalytic cracking slurry

The above examples and the results of deashing performance evaluation show that the slurry settlers in the present application have wide applicability, and although the removal rate of yue first YS-4015 in daqing refining catalytic cracking slurry is higher than that of some examples in the present application, the application is poor. The crude oil adopted by each refinery is not completely fixed, and can be selected and purchased according to market price and different actual components of crude oil in each region; refineries also blend a certain amount of atmospheric, coker gas oil and vacuum residuum in the catalytically cracked slurry at irregular intervals, which results in a large variation in the composition of the catalytically cracked slurry and the ash content, and requires testing and selection of new slurry settlers simultaneously.

The catalytic cracking slurry oil settling agent provided by the invention considers three characteristics of dissolution dispersion, electricity elimination agglomeration and flocculation settling of the settling agent, is suitable for catalytic cracking slurry oil with different compositions and different ash contents, can be used under a wider dosage and settling temperature, and is easy to popularize and use on a large scale. In addition, the method avoids the increase of management cost and operation cost caused by the need of simultaneously storing different types of slurry settling agents when a refinery changes the crude oil source and performs blending on the catalytic cracking slurry. The above problems are eliminated after the slurry settling agent of the present application is used.