CN112094673A

CN112094673A - High-temperature dispersing agent for heavy oil deep processing device and preparation and application thereof

Info

Publication number: CN112094673A
Application number: CN202011017742.7A
Authority: CN
Inventors: 蒋云超; 戈杰; 郑立军
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-09-24
Filing date: 2020-09-24
Publication date: 2020-12-18
Anticipated expiration: 2040-09-24
Also published as: CN112094673B

Abstract

The invention relates to a high-temperature dispersing agent for a heavy oil deep processing device, and preparation and application thereof. The high-temperature dispersant comprises: 30-60 parts by weight of tall oil fatty acid and maleic anhydride copolymer, 10-30 parts by weight of isobutylene and maleic anhydride copolymer and 30-60 parts by weight of aromatic solvent oil with the boiling point range of 160-240 ℃. The high-temperature dispersing agent disclosed by the invention is stable and not easy to decompose at high temperature, can adapt to the high-temperature characteristic of a heavy oil deep processing device, can effectively inhibit precipitation and deposition of scales, disperses the scales existing in a system, prolongs the production operation period of the device, maintains the heat exchange efficiency and improves the economic benefit of the device.

Description

High-temperature dispersing agent for heavy oil deep processing device and preparation and application thereof

Technical Field

The application belongs to the field of heavy oil deep processing production, and relates to a high-temperature dispersing agent of a heavy oil deep processing device, and preparation and application thereof.

Background

The deep processing of heavy oil (including heavy oil such as diesel oil, wax oil, atmospheric and vacuum residue oil, coal tar, ethylene tar, styrene tar, oil slurry and the like) can greatly improve the economic benefit of an oil refinery. The deep processing technology of heavy oil comprises the following steps: catalytic cracking, fixed bed hydrogenation, fluidized bed hydrogenation, delayed coking, and the like. However, heavy oil contains a large amount of asphaltenes, colloids, organic polymers, metal impurities, corrosion by-products, salts, solid impurities, and the like. In the deep processing process of heavy oil, scale can be separated out from parts such as a heat exchanger, a tower, a heating furnace, a pipeline and the like, so that the problems of increased energy consumption of the device, reduced load, reduced yield of target products, greatly shortened operation period of the device, increased parking and cleaning cost, increased influence on safety and environmental protection and the like are caused.

At present, there are two main methods for solving the problems, one is to adopt a process and an equipment method: the method is realized by mainly increasing auxiliary equipment, improving the process flow and the operating conditions, controlling the property index of the raw oil and the like; the other method is a chemical method, and a certain amount of chemical auxiliary agents are usually added into raw oil to inhibit and delay the formation of coke on the surface of equipment. The latter method has the advantages of no change of process flow, no influence on normal operation, convenient and flexible filling, low capital investment, short recovery period and the like, so that the method becomes an economic and effective method for solving the coking and fouling problems of equipment.

Aiming at the scaling problem of heavy oil in the deep processing process, the use of a proper dispersant is an effective method for effectively controlling the scaling problem of the system. Some work is also carried out in recent years in China, but due to the fact that the temperature of a scaling part is high, a common additive can be decomposed and lose efficacy under the high-temperature condition, and the purpose of really and effectively inhibiting the scaling of a process system cannot be achieved. And the chemical auxiliary products developed in recent years are mainly composed of sulfur-containing compounds, phosphorus-containing compounds or boron-containing chemicals, so that the catalyst in the processing process is poisoned, and the equipment is corroded to a certain extent after high-temperature decomposition, thereby increasing the coking. In patent US5183555A polyisobutylene succinimide or derivatives thereof are used for dispersing and solubilising the formed coke scale. US4927519 discloses the use of polysulphurized alkylphenol compounds for inhibiting the formation of coke. However, these products have poor thermal stability and their effectiveness decreases above 300 ℃. The additive for improving the yield of the light oil of the delayed coking device and the preparation method thereof provided by the patent CN1560198A have the additive combination consisting of a thermal cracking active substance, a free radical chain reaction inhibitor, an anti-coking agent, a solvent and the like, and have undesirable effects on reducing scaling and coking of solid substances adhered to the surface of equipment and inhibiting the generation of coke due to the lack of a high-temperature dispersant.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a high-temperature dispersing agent for a heavy oil deep processing device, and preparation and application thereof, so as to improve the stability of the high-temperature dispersing agent in the heavy oil processing process, ensure that the high-temperature dispersing agent is not easy to decompose and lose efficacy under the high-temperature working condition, and effectively inhibit scaling on the surfaces of high-temperature process equipment, such as heat exchange equipment, towers, pipelines, heating furnaces and the like.

The invention provides a high-temperature dispersant for a heavy oil deep processing device, which comprises the following components in parts by weight: 30-60 parts of a component A, 10-30 parts of a component B and 30-60 parts of a component C;

the component A is a tall oil fatty acid and maleic anhydride copolymer with at least one of molecular weight of 1500-; the component B is a copolymer of isobutene and maleic anhydride and has the molecular weight of at least one of 600-1000, 1200-2000 and 2200-3000; the C component is aromatic solvent oil with the boiling point range of 160-240 ℃.

Further, the high-temperature dispersing agent for the heavy oil deep processing device preferably comprises 40-50 parts by weight of a component A, 10-15 parts by weight of a component B and 45-55 parts by weight of a component C; the component A is tall oil fatty acid and maleic anhydride copolymer with the molecular weight of 4000-; the component B is a copolymer of isobutene and maleic anhydride, and the molecular weight is 2200-3000; the component C is mixed trimethylbenzene.

Further, the weight ratio of tall oil fatty acid to maleic anhydride is 60-80: 10-20 parts of; the weight ratio of isobutene to maleic anhydride is 40-60: 20-40.

The invention also provides a preparation method of the high-temperature dispersing agent for the heavy oil deep processing device, which comprises the following steps:

(1) preparing a component A tall oil fatty acid and maleic anhydride copolymer;

(2) preparing a copolymer of isobutene and maleic anhydride as the component B;

(3) under the condition of continuous stirring, uniformly mixing the component A, the component B and the component C according to the feeding ratio to obtain the high-temperature dispersing agent.

The molecular weight of the A component tall oil fatty acid and maleic anhydride copolymer in the step (1) is at least one of 1500-; the weight ratio of the tall oil fatty acid to the maleic anhydride is 60-80: 10-20.

The molecular weight of the B component copolymer of isobutene and maleic anhydride in the step (2) is at least one of 600-1000, 1200-2000 and 2200-3000, preferably 2200-3000; the weight ratio of the isobutene to the maleic anhydride is 40-60: 20-40.

The feeding ratio of the component A, the component B and the component C in the step (3) is 30-60 in parts by weight: 10-30: 30-60, preferably 40-50: 10-15: 45-55; in the step (3), the component C is aromatic solvent oil with the boiling point range of 160-240 ℃, and preferably mixed trimethylbenzene.

The preparation method in the step (1) or (2) is that the raw materials are respectively dissolved in a solvent, sequentially added into a reaction kettle, nitrogen is filled, meanwhile, an initiator benzoyl peroxide is dripped, continuously stirred, reacted at a reaction temperature, an amber sticky substance is formed in the kettle, taken out, filtered and weighed to obtain the product; the dosage of the initiator benzoyl peroxide is 0.5 to 1 percent of the mass of the raw material; the reaction temperature is 100-120 ℃, and the reaction time is 4-8 h. The solvent is a solvent capable of dissolving raw materials and is one or more of ethyl acetate, toluene and N, N-Dimethylformamide (DMF).

The invention also provides application of the high-temperature dispersing agent of the heavy oil deep processing device. The mass concentration of the high-temperature dispersant added is 10 to 1000ppm, preferably 30 to 600ppm, based on the amount of processed heavy oil. The injection mode is that the high-temperature dispersing agent is continuously injected into the heavy oil raw material on line in an upstream pipeline of the easy-scaling equipment. The application range of the high-temperature dispersing agent is a heavy oil deep processing device with the temperature not exceeding 500 ℃. The heavy oil deep processing device comprises a reactor, a heat exchanger, a reboiler, a preheater, a condenser, a heating furnace, a pump, a filter, a process pipeline and a tower.

The high-temperature dispersing agent is stable and not easy to decompose at high temperature, can adapt to the high-temperature characteristic of heavy oil deep processing devices, effectively inhibits the condensation growth of colloid and asphaltene, avoids the deposition of organic matters (olefin polymers, colloid and asphaltene) and inorganic matters (catalyst dust, coke powder, corrosion byproducts, salts, metal oxides, sulfides and the like), and effectively disperses the scale existing in the system, so that the scale is kept in a suspension state and is not deposited in process material flows, and the scale is prevented from being separated out at parts such as heat exchangers, towers, heating furnaces, pipelines and the like. The effects of prolonging the production operation period of the device, keeping the heat exchange efficiency and improving the economic benefit of the device are achieved. The invention can bring remarkable economic, environmental and social benefits for heavy oil deep processing devices, such as catalytic cracking, fixed bed hydrogenation, fluidized bed hydrogenation, delayed coking and the like.

Description of the drawings:

FIG. 1: simulated effect of high temperature dispersant under high temperature operating condition.

The specific implementation mode is as follows:

examples 1 to 8 and comparative examples 1 to 2 are respective components, ratios and preparation examples of the high-temperature dispersant for the heavy oil deep processing device. Examples 9-15 are examples of dispersing effects at different standing times. Example 16 and comparative examples 3 to 4 are examples of the effect of application in a high temperature state. The molecular weight test of the copolymer in the examples and comparative examples was determined by gel permeation chromatography.

Example 1

(1) Respectively dissolving 60 parts by weight of tall oil fatty acid and 10 parts by weight of maleic anhydride in DMF, sequentially adding into a reaction kettle, introducing nitrogen, simultaneously dropwise adding initiator benzoyl peroxide accounting for 0.5% of the raw material, stirring continuously, and reacting for 6h at 120 ℃. The kettle is an amber sticky substance, which is taken out, filtered and weighed to obtain the component A tall oil fatty acid and maleic anhydride copolymer with the molecular weight of 2000.

(2) Respectively dissolving 40 parts by weight of isobutene and 20 parts by weight of maleic anhydride in DMF, sequentially adding into a reaction kettle, introducing nitrogen, simultaneously dropwise adding an initiator benzoyl peroxide accounting for 0.8 percent of the raw material, continuously stirring, and reacting for 6 hours at 100 ℃. The kettle is an amber sticky substance, which is taken out, filtered and weighed to obtain the component B copolymer of isobutylene and maleic anhydride with the molecular weight of 800.

(3) Under the condition of continuous stirring, the feeding ratio of the component A, the component B and the component C is 45 in parts by weight: 15: 45, uniformly mixing the tall oil fatty acid component A and the maleic anhydride copolymer, the isobutylene component B and the maleic anhydride copolymer, and the mixed trimethylbenzene component C to obtain the high-temperature dispersing agent S1.

And (3) testing the dispersibility: 50g of coke blocks in a preheater (the process operation temperature is more than 250 ℃) of a certain domestic residual oil hydrogenation device are dried for 2 hours at a constant temperature in a constant temperature furnace at 105 ℃. Taking out, and grinding into fine powder. 1g of the treated powdery scale sample is put into a test tube, 200ml of n-heptane is added, 200ppm of high-temperature dispersing agent S1 is added, the mixture is uniformly shaken up and down for 2 minutes, and after standing for 5 minutes, the weight of the scale deposited at the bottom of the test tube is weighed to judge the effect of the high-temperature dispersing agent, which is shown in Table 3.

Examples 2 to 8, comparative examples 1 to 2

The difference from example 1 is that the high temperature dispersant composition is as shown in table 1. The results of the dispersibility tests are shown in Table 3.

Examples 9 to 15

The dispersibility test conditions are the same as those of the dispersibility test condition of the example 1, except that the high-temperature dispersing agent S5 of the example 5 is taken to carry out the dispersibility test with different standing times. The effect of different standing times on the dispersing effect is shown in table 2.

Table 1: high-temperature dispersant composition for heavy oil deep processing device

Table 2: influence of different standing times on the dispersing effect

	Standing time/min	Settled sludge mass/g
			Example 9	5	0.22
Example 10	10	0.27
			Example 11	15	0.35
Example 12	20	0.46
			Example 13	25	0.58
Example 14	30	0.58
			Example 15	40	0.58

Table 3: results of dispersibility test of high-temperature dispersant for heavy oil deep-processing apparatuses of examples 1 to 8 and comparative examples

	Settled sludge mass/g
		Example 1	0.89
Example 2	0.82
		Example 3	0.55
Example 4	0.41
		Example 5	0.22
Example 6	0.85
		Example 7	0.63
Example 8	0.57
		Comparative example 1	0.95
Comparative example 2	0.92

Example 16 and comparative examples 3 to 4

The high-temperature dispersants S5, D1 and D2 are tested for simulation effect test under high-temperature operation state according to the composition in Table 1.

The heavy oil raw material is atmospheric residue of a certain domestic device. The initial outlet operating temperature of the heat exchange tube is set to be 550 ℃, the test period is 60 days, the change of the outlet temperature of the heat exchange tube is measured every day, and the mass concentration of the high-temperature dispersing agent is 100ppm based on the processing amount of the heavy oil. Under the condition of high temperature of raw materials in the heat exchange tube, along with the extension of operation time, scaling can become serious day by day, so that the heat exchange efficiency is reduced, the temperature of the outlet of the heat exchange tube is gradually reduced, and the dispersing effect of different dispersing agents at high temperature is judged according to the temperature reduction rate. The results are shown in FIG. 1.

As shown in the table 3, the results of the dispersion test of the high-temperature dispersant for heavy oil deep processing devices show that, under the same test conditions, the weight of the deposited scale in the examples 1-8 is smaller than that in the comparative examples 1-2, and the dispersion effect is obviously better than that in the comparative examples. As shown in Table 2, examples 9 to 15 show that the dispersion effect is stable and the particles are not easy to agglomerate and deposit as the standing time is prolonged.

As can be seen from FIG. 1, the effect of example 16 is superior to the simulation effect of comparative examples 3-4 in the high-temperature operation state, and the outlet temperature of the heating pipe is higher than that of comparative example 20 ℃. The dispersing agent has high heat exchange efficiency in practical application, can well disperse heavy oil raw materials, and is not easy to scale.

Claims

1. The high-temperature dispersing agent for the heavy oil deep processing device is characterized by comprising the following components in parts by weight: 30-60 parts of a component A, 10-30 parts of a component B and 30-60 parts of a component C;

the component A is a tall oil fatty acid and maleic anhydride copolymer with at least one of molecular weight of 1500-;

the component B is a copolymer of isobutene and maleic anhydride and has the molecular weight of at least one of 600-1000, 1200-2000 and 2200-3000;

the C component is aromatic solvent oil with the boiling point range of 160-240 ℃.

2. The high-temperature dispersant for heavy oil deep processing devices according to claim 1, comprising 40 to 50 parts by weight of component A, 10 to 15 parts by weight of component B and 45 to 55 parts by weight of component C;

the component A is tall oil fatty acid and maleic anhydride copolymer with the molecular weight of 4000-;

the component B is a copolymer of isobutene and maleic anhydride, and has a molecular weight of 2200-3000;

the component C is mixed trimethylbenzene.

3. The high temperature dispersant for heavy oil deep processing unit according to any one of claims 1-2, wherein the weight ratio of tall oil fatty acid to maleic anhydride is 60-80: 10-20.

4. The high-temperature dispersant for heavy oil deep processing equipment according to any one of claims 1 to 2, wherein the weight ratio of isobutylene to maleic anhydride is 40 to 60: 20-40.

5. The method for preparing the high-temperature dispersant of the heavy oil deep processing device as claimed in any one of claims 1 to 4, characterized by comprising the following steps:

(1) preparing a component A tall oil fatty acid and maleic anhydride copolymer;

(2) preparing a copolymer of isobutene and maleic anhydride as the component B;

6. The method for preparing high-temperature dispersant for heavy oil deep processing device according to claim 5, characterized in that the molecular weight of said A component tall oil fatty acid and maleic anhydride copolymer in step (1) is at least one of 1500-; the weight ratio of the tall oil fatty acid to the maleic anhydride is 60-80: 10-20.

7. The method for preparing high-temperature dispersant for heavy oil deep processing device according to claim 5, wherein the molecular weight of said B component copolymer of isobutylene and maleic anhydride in step (2) is at least one of 600-; the weight ratio of the isobutene to the maleic anhydride is 40-60: 20-40.

8. The method for preparing the high-temperature dispersant of the heavy oil deep processing device according to claim 5, wherein the feeding ratio of the component A, the component B and the component C in the step (3) is 30-60: 10-30: 30-60, preferably 40-50: 10-15: 45-55.

9. The method for preparing the high-temperature dispersant of the heavy oil deep processing device according to claim 5, wherein the preparation method in step (1) or (2) is that the raw materials are respectively dissolved in a solvent, sequentially added into a reaction kettle, filled with nitrogen, simultaneously added with an initiator benzoyl peroxide dropwise, continuously stirred, reacted at a reaction temperature, and the kettle is an amber viscous substance, taken out, filtered and weighed to obtain the high-temperature dispersant; the dosage of the initiator benzoyl peroxide is 0.5 to 1 percent of the mass of the raw material; the reaction temperature is 100-120 ℃, and the reaction time is 4-8 h.

10. Use of the high-temperature dispersant for heavy oil further processing equipment according to any one of claims 1 to 4, wherein the added mass concentration is 10 to 1000ppm, preferably 30 to 600ppm, based on the processed amount of the heavy oil.