阅读说明：本技术 重油流态化加工原料的预处理剂以及预处理方法 (Pretreating agent and pretreating method for heavy oil fluidized processing raw material ) 是由 刘必心 张书红 任磊 李延军 李子锋 陈昱 于 2018-06-15 设计创作，主要内容包括：本发明涉及石油加工领域,公开了一种重油流态化加工原料的预处理剂,其中,以所述预处理剂的总重量为基准,该预处理剂含有1-35重量％的组分A和65-99重量％的溶剂；所述组分A的通式为[Si(CH<Sub>3</Sub>)<Sub>3</Sub>]<Sub>m</Sub>L,L为卤原子或N<Sub>a</Sub>H<Sub>b</Sub>C<Sub>c</Sub>O<Sub>d</Sub>(CR<Sub>3</Sub>)<Sub>e</Sub>,其中,R为氢原子或者卤原子,a、b、c、d、e和m各自独立地为0-3的任一整数。本发明还公开了一种重油流态化加工原料的预处理方法。采用本发明提供的预处理剂对重油进行预处理,可以使重油的粘度得到有效降低,并且经过处理后的重油在固定流化床中进行流态化接触裂化反应后,与未处理的重油相比,生焦率也得到降低。(The invention relates to the field of petroleum processing and discloses a pretreating agent for a fluidized processing raw material of heavy oil, wherein the pretreating agent comprises 1-35 wt% of a component A and 65-99 wt% of a solvent based on the total weight of the pretreating agent; the component A has a general formula of [ Si (CH) 3 ) 3 ] m L and L are halogen atoms or N a H b C c O d (CR 3 ) e Wherein R is a hydrogen atom or a halogen atom, and a, b, c, d, e and m are each independently any integer of 0 to 3. The invention also discloses a pretreatment method of the heavy oil fluidized processing raw material. The heavy oil is pretreated by the pretreating agent provided by the invention, the viscosity of the heavy oil can be effectively reduced, and the treated heavy oil flows in a fixed fluidized bedAfter the fluidization contact cracking reaction, the coke rate is also reduced compared with untreated heavy oil.)

1. A pretreating agent for a fluidized raw material for processing heavy oil, characterized by comprising 1 to 35% by weight of component A and 65 to 99% by weight of a solvent, based on the total weight of the pretreating agent; the component A has a general formula of [ Si (CH)₃)₃]_mL and L are halogen atoms or N_aH_bC_cO_d(CR₃)_eWherein R is a hydrogen atom or a halogen atom, and a, b, c, d, e and m are each independently any integer of 0 to 3.

2. The pretreating agent according to claim 1, wherein the pretreating agent comprises 2 to 30% by weight of said component a and 70 to 98% by weight of a solvent, based on the total weight of the pretreating agent.

3. The pretreating agent according to claim 1 or 2, wherein in the component A, R is a hydrogen atom or a fluorine atom.

4. The pretreating agent of claim 3, wherein component A is selected from at least one of N, O-bis (trimethylsilane) trifluoroacetamide, N, O-bis (trimethylsilane) acetamide, N-methyl-N- (trimethylsilane) trifluoroacetamide, hexamethyldisilazane, N-diethylaminotrimethylsilane, trimethylsilyldiethylamine, trimethylsilylimidazole, tert-butyldimethylchlorosilane, and trimethylchlorosilane.

5. The pretreating agent of claim 4, wherein component A is N, O-bis (trimethylsilane) trifluoroacetamide, N, O-bis (trimethylsilane) acetamide, N-methyl-N- (trimethylsilane) trifluoroacetamide, or trimethylsilylimidazole, or;

the component A is a combination of any two, preferably, the weight ratio of the two is 1: 0.05-20; more preferably, the component A is a combination of trimethylchlorosilane and hexamethyldisilazane, and the weight ratio of the trimethylchlorosilane to the hexamethyldisilazane is 1:0.05-20, preferably 1: 1-10; or the component A is a combination of trimethylsilyldiethylamine and tert-butyldimethylchlorosilane, and the weight ratio of the trimethylsilyldiethylamine to the tert-butyldimethylchlorosilane is 1:0.05-20, preferably 1: 1-10.

6. The pretreating agent according to claim 1 or 2, wherein the solvent is selected from at least one of water, toluene, tetrahydrofuran, dichloromethane, and dimethylformamide.

7. A method for pretreating a fluidized processing raw material of heavy oil, comprising: mixing heavy oil with a pretreating agent according to any one of claims 1 to 6 in an inert atmosphere and under stirring, and carrying out a reflux stirring reaction.

8. The pretreatment method according to claim 7, wherein the pretreating agent is used in an amount of 0.05 to 15% by weight based on the weight of the heavy oil.

9. The pretreatment method according to claim 8, wherein the pretreating agent is used in an amount of 0.1 to 12% by weight based on the weight of the heavy oil.

10. The pretreatment method according to any one of claims 7 to 9, wherein a mixing temperature of the heavy oil and the pretreatment agent is 40 to 180 ℃, preferably 50 to 150 ℃; the temperature of the reflux stirring reaction is 40-180 ℃, preferably 50-150 ℃, and the reaction time is 3-35h, preferably 5-25 h.

Technical Field

The invention relates to a pretreating agent and a pretreating method for a fluidized processing raw material of heavy oil.

Background

With the development of the petroleum industry, aiming at the increasing weight of petroleum resources and the requirement of environment-friendly fuel oil products, a great deal of research work is carried out on how to improve the yield of liquid products, reduce the yield of coke and the like by various large petroleum companies and scientific research institutions at home and abroad around the problem of high-efficiency utilization of heavy oil. In recent years, the development of heavy oils, the processing and application of heavy oils, has become increasingly important in the petroleum industry. Most of the crude oil in China is heavy oil, and the content of the heavy oil is 40-50 wt% or more. In heavy oil which is continuously mined in recent years, the content of the reduced pressure heavy oil is 60 wt% or more, for example, the content of the reduced pressure heavy oil in single mosque heavy oil is 65.6 wt%. Compared with other distillate oil, the heavy oil has high content of colloid and asphaltene, and the colloid and asphaltene molecules can form high-regularity aggregates in the heavy oil. When the aggregate is displaced relatively, a large internal friction force is generated, so that the heavy oil shows a high viscosity.

The fluidized processing of heavy oil is an important technical means for treating heavy oil, and includes technologies such as fluid coking, flexicoking, HTL, catalytic cracking and the like. In the fluidization processing process, the atomization condition and the gasification degree of the raw oil play a very important role in the fluidization processing. Taking catalytic cracking as an example, if the viscosity of the raw oil is too high, the overall atomization effect of the raw material is affected, so that the thickness of an oil film attached to a catalyst is increased, the gasification degree of the raw oil is further affected, the effect of a condensation reaction is enhanced, the coke yield is too high, the coke burning load of a regenerator is large, and the energy consumption of a device is increased. Therefore, the raw material heavy oil for fluidized processing of the heavy oil is pretreated, the viscosity of a heavy oil system is reduced, colloid and asphaltene aggregates in the heavy oil system are broken, and further fluidized processing and utilization of the heavy oil are necessary.

For the pretreatment of heavy oil as a raw material for fluidized processing of heavy oil, three treatment modes such as hydrogenation, emulsification and ultrasonic treatment are mainly adopted at present.

After the heavy oil is subjected to hydrogenation pretreatment, the cracking performance of the raw material can be improved, the coking tendency under high conversion rate can be reduced, the yield of light products can be increased, the sulfur content of the products can be reduced, the sulfur content in flue gas can be reduced, and the capacity of a device for processing inferior raw materials can be improved. However, the raw oil hydrogenation pretreatment device has slightly large investment and slightly high operation cost. For example, CN1335371A discloses a heavy hydrocarbon feedstock hydrotreating method, which organically combines the thermal hydrocracking technology of heavy oil with the fixed bed heavy oil hydrotreating technology, wherein the heavy hydrocarbon feedstock is first subjected to mild thermal hydrocracking pretreatment in a suspended bed or similar reactor, and then enters a fixed bed hydrotreating apparatus for hydrotreating.

In order to improve the atomization effect of heavy oil in the fluidization processing process, some researchers develop a cold-feed fluidization reaction process of an emulsified raw material according to a micro-explosion theory and a molecular aggregation and depolymerization theory in the emulsification combustion process of the heavy oil. The purpose is to reduce the viscosity of heavy oil and facilitate the atomization of raw materials. For example, CN1356373A discloses an emulsion feeding method for heavy oil catalytic cracking, which adopts a unique secondary "blasting" atomization technique to improve the atomization effect and greatly improve the contact between the raw material and the catalyst. The technology mainly changes the physical property of the catalytic cracking raw oil before entering a riser reactor in an emulsifying mode so that the catalytic cracking raw oil is in full contact with a high-temperature catalyst in the riser reactor and generates secondary blasting atomization, thereby achieving the purposes of improving the reaction depth, improving the product distribution and improving the target product yield, and is characterized in that the raw oil is emulsified by adopting a non-ionic emulsifier, and the catalytic cracking raw oil is prepared into water-in-oil type emulsified oil at the temperature of 60-80 ℃. And an emulsified feeding method is adopted, and the emulsified catalytic cracking raw oil is sprayed into the riser reactor in an atomized state through a nozzle at the temperature of 150 ℃. The test result shows that after the emulsification feeding is adopted, under the same reaction condition, the conversion rate of the emulsified oil in the normal slag is improved by about 5 percent compared with the normal slag, the yield of the dry gas is improved by 0.8 percent, and the yield of the coke is reduced by about 1 percent compared with the normal slag.

CN103805229A discloses a raw material pretreatment method for improving the lightweight property of heavy oil. The method utilizes the cavitation and composite action of ultrasonic waves to change the colloid structure of the heavy oil, optimize the structural composition of the heavy oil, promote the uniform distribution of four components, improve the stability of a colloid system, generally improve the quality of the heavy oil and obviously improve the hydrogenation effect of the heavy oil. The ultrasonic treatment effect of heavy oil from different sources is greatly different. According to the data after the hydrogenation treatment, the method reduces the average relative molecular mass of the reduced pressure heavy oil by 3-6%, reduces the viscosity by 5-12%, reduces the carbon residue value by about 21-40%, improves the heavy oil conversion rate by 8-10% after the hydrogenation, improves the light oil yield by 7-11%, and the like. The method for treating the heavy oil by the ultrasonic waves is also used for reducing the viscosity of a heavy oil system, so that a better atomization effect is achieved, and the coking rate of the reaction is further reduced. The principle analysis shows that the viscosity of the heavy oil after ultrasonic treatment is temporarily reduced, and the viscosity of the heavy oil system can be further recovered after a period of time.

CN102643670A discloses a pretreatment method of heavy oil raw material, which comprises adding a proper amount of free radical terminator into the heavy oil raw material, and introducing the mixture into a thermal conversion reactor for mild thermal conversion; the thermally converted stream enters the contact cracking reactor and the coke yield decreases after the reaction, a process similar to the hydrode-stick technology.

Therefore, the existing pretreatment method for the heavy oil fluidized processing raw material has some problems, for example, although the effect of the pretreatment is good, the cost is high; although emulsification has a certain effect, the added emulsifier can have a certain influence on the oil-water separation of the final product; the heavy oil after the ultrasonic treatment is temporarily reduced in viscosity. Therefore, there is a need to provide a new heavy oil pretreatment process that fundamentally reduces the viscosity of the heavy oil, thereby improving the cracking performance of the heavy oil and reducing the propensity for coking at high conversion rates.

Disclosure of Invention

The invention aims to overcome the defects of the conventional pretreatment method of the fluidized processing raw material of the heavy oil and provide a novel pretreatment agent and a pretreatment method of the fluidized processing raw material of the heavy oil.

In order to achieve the above object, in one aspect, the present invention provides a pretreating agent for a fluidized raw material for heavy oil processing, wherein the pretreating agent comprises component a in an amount of 1 to 35% by weight and a solvent in an amount of 65 to 99% by weight, based on the total weight of the pretreating agent; the component A has a general formula of [ Si (CH)₃)₃]_mL and L are halogen atoms or N_aH_bC_cO_d(CR₃)_eWherein R is a hydrogen atom or a halogen atom, and a, b, c, d, e and m are each independently any integer of 0 to 3.

Preferably, the component a is selected from at least one of N, O-bis (trimethylsilane) trifluoroacetamide, N, O-bis (trimethylsilane) acetamide, N-methyl-N- (trimethylsilane) trifluoroacetamide, hexamethyldisilazane, N-diethylaminotrimethylsilane, trimethylsilyldiethylamine, trimethylsilylimidazole, tert-butyldimethylchlorosilane, and trimethylchlorosilane.

Preferably, the component a is N, O-bis (trimethylsilane) trifluoroacetamide, N, O-bis (trimethylsilane) acetamide, N-methyl-N- (trimethylsilane) trifluoroacetamide, or trimethylsilylimidazole, or;

the component A is a combination of any two, preferably, the weight ratio of the two is 1: 0.05-20; more preferably, the component A is a combination of trimethylchlorosilane and hexamethyldisilazane, the weight ratio of the trimethylchlorosilane to the hexamethyldisilazane is 1:0.05-20, more preferably 1: 1-10; or the component A is a combination of trimethylsilyldiethylamine and tert-butyldimethylchlorosilane, and the weight ratio of the trimethylsilyldiethylamine to the tert-butyldimethylchlorosilane is 1:0.05-20, and more preferably 1: 1-10.

In a second aspect, the present invention provides a method for pretreating a fluidized raw material for processing heavy oil, wherein the method comprises: the method comprises the following steps: mixing heavy oil and a pretreating agent in an inert atmosphere under stirring, and carrying out reflux stirring reaction, wherein the pretreating agent is the pretreating agent disclosed by the invention.

The heavy oil raw material has high viscosity and difficult atomization, colloid and asphaltene molecules can form an aggregate with high regularity in the heavy oil, and the relative displacement between the molecules of the crude oil can generate great internal friction force, so that the high viscosity of the heavy oil is shown, and the colloid and the asphaltene molecules are difficult to gasify and are greatly condensed into coke when contacting with a catalyst no matter the high viscosity of the heavy oil is shown macroscopically or the colloid and the asphaltene aggregate are formed microscopically. The heavy oil pretreatment agent and the pretreatment method thereof provided by the invention have the advantages that the heavy oil is pretreated before entering the reactor, the viscosity of the heavy oil is reduced, the heavy oil can better react with a catalyst after entering the reactor, and the yield of coke is reduced.

More specifically, after the heavy oil is treated by the pretreating agent, the aggregation of colloid and asphaltene is broken, the viscosity of the heavy oil is fundamentally reduced, the heavy oil is easier to atomize when entering a reactor, the reaction efficiency after the heavy oil is contacted with a catalyst is enhanced, and the coke yield is further reduced.

The pretreating agent provided by the invention is used for pretreating heavy oil, so that the viscosity of the heavy oil can be effectively reduced, and the coking rate of the treated heavy oil is reduced compared with untreated heavy oil after fluidized contact cracking reaction of the treated heavy oil in a fixed fluidized bed.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

According to the present invention, the pretreating agent for a fluidized raw material for heavy oil processing comprises, based on the total weight of the pretreating agent, 1 to 35% by weight of component A and 65 to 99% by weight of a solvent. Preferably, the content of the component A is 2 to 30% by weight and the content of the solvent is 70 to 98% by weight based on the total weight of the pretreating agent.

According to the invention, component A has the general formula [ Si (CH)₃)₃]_mL and L are halogen atoms (F, Cl, Br, I) or N_aH_bC_cO_d(CR₃)_eWherein R is a hydrogen atom or a halogen atom (F, Cl, Br, I), preferably R is a hydrogen atom or a fluorine atom; a. b, c, d, e and m are each independently any integer from 0 to 3.

According to the invention, preferably, L in the component A is N_aH_bC_cO_d(CR₃)_eWhen R is a hydrogen atom or a fluorine atom, the component A is at least one of N, O-bis (trimethylsilane) trifluoroacetamide, N, O-bis (trimethylsilane) acetamide, N-methyl-N- (trimethylsilane) trifluoroacetamide, hexamethyldisilazane, N-diethylaminotrimethylsilane, trimethylsilyldiethylamine, trimethylsilylimidazole and tert-butyldimethylchlorosilane.

According to the invention, preferably, when L in the component a is a halogen atom, preferably a chlorine atom, the component a is trimethylchlorosilane.

Therefore, in the present invention, more preferably, the component a is at least one of bis N, O-bis (trimethylsilane) trifluoroacetamide, N, O-bis (trimethylsilane) acetamide, N-methyl-N- (trimethylsilane) trifluoroacetamide, hexamethyldisilazane, N-diethylaminotrimethylsilane, trimethylsilyldiethylamine, trimethylsilylimidazole, tert-butyldimethylchlorosilane, and trimethylchlorosilane.

According to the present invention, preferably, the component a is N, O-bis (trimethylsilane) trifluoroacetamide, N, O-bis (trimethylsilane) acetamide, N-methyl-N- (trimethylsilane) trifluoroacetamide or trimethylsilylimidazole.

Specifically, according to an embodiment of the present invention, the pretreating agent comprises 1-35 wt% of N, O-bis (trimethylsilane) trifluoroacetamide and 65-99 wt% of a solvent, based on the total weight of the pretreating agent for the fluidized raw material for heavy oil processing.

According to an embodiment of the present invention, the pretreating agent comprises 1-35 wt% of trimethylsilylimidazole and 65-99 wt% of a solvent, based on the total weight of the pretreating agent.

According to an embodiment of the present invention, the pretreating agent comprises 1-35 wt% of N, O-bis (trimethylsilane) acetamide and 65-99 wt% of a solvent, based on the total weight of the pretreating agent for the fluidized raw material for processing heavy oil.

According to an embodiment of the present invention, the pretreating agent comprises 1-35 wt% of N-methyl-N- (trimethylsilane) trifluoroacetamide and 65-99 wt% of a solvent, based on the total weight of the pretreating agent for the fluidized raw material for processing heavy oil.

According to the present invention, preferably, the component a is a combination of any two of bis N, O-bis (trimethylsilane) trifluoroacetamide, N, O-bis (trimethylsilane) acetamide, N-methyl-N- (trimethylsilane) trifluoroacetamide, hexamethyldisilazane, N-diethylaminotrimethylsilane, trimethylsilyldiethylamine, trimethylsilylimidazole, tert-butyldimethylchlorosilane, and trimethylchlorosilane, more preferably, the weight ratio of the two is 1:0.05 to 20.

Specifically, according to an embodiment of the present invention, the pretreating agent comprises 1-15 wt% of trimethylchlorosilane, 1-20 wt% of hexamethyldisilazane, and 65-99 wt% of a solvent, based on the total weight of the pretreating agent for the fluidized raw material for processing heavy oil. More preferably, the weight ratio of trimethylchlorosilane to hexamethyldisilazane is from 1:0.05 to 20, more preferably from 1:1 to 10.

According to an embodiment of the present invention, the pretreating agent comprises 1-20 wt% of t-butyldimethylsilyl chloride and 1-15 wt% of trimethylsilyl diethylamine, and 65-99 wt% of a solvent, based on the total weight of the pretreating agent of the fluidized raw material for processing heavy oil. More preferably, the weight ratio of trimethylsilyldiethylamine to t-butyldimethylchlorosilane is 1:0.05 to 20, and more preferably 1:1 to 10.

According to the present invention, the solvent may be a solvent each capable of dissolving component a in the art, and preferably, the solvent is at least one of toluene, tetrahydrofuran, and dichloromethane. More preferably, the solvent is at least one of toluene, tetrahydrofuran and dichloromethane.

According to the present invention, the component a and the solvent are added in such amounts that the content of the component a is 1 to 35% by weight and the content of the solvent is 65 to 99% by weight, based on the total weight of the pretreating agent, preferably such that the content of the component a is 2 to 30% by weight and the content of the solvent is 70 to 98% by weight.

Wherein the component A and the solvent are as described above, and are not described in detail herein.

According to the invention, the pretreatment method of the heavy oil fluidized processing raw material comprises the following steps: mixing heavy oil and a pretreating agent in an inert atmosphere under stirring, and carrying out reflux stirring reaction, wherein the pretreating agent is the pretreating agent provided by the invention.

According to the present invention, the pretreating agent (the total mass of component A and the solvent) is used in an amount of 0.05 to 15% by weight, more preferably 1 to 12% by weight, based on the weight of the heavy oil. Although the pretreatment agent provided by the invention can effectively reduce the viscosity of the heavy oil, and the heavy oil can better react with the catalyst after entering the reactor, thereby reducing the yield of coke, the pretreatment agent can achieve better pretreatment effect on the heavy oil within the preferable range.

In the method for pretreating a fluidized raw material for processing heavy oil according to the present invention, preferably, the pretreating agent is mixed with heavy oil at a temperature of 40 to 180 ℃, more preferably 50 to 150 ℃; the reflux stirring temperature of the heavy oil and the pretreating agent is preferably 40-180 ℃, more preferably 50-150 ℃, and the reflux stirring reaction time is preferably 3-35h, more preferably 5-25 h. Under the preferred mixing and refluxing reaction conditions, the pretreatment agent can be fully interacted with the heavy oil, so that the pretreatment agent can play a better pretreatment role.

According to the invention, the inert atmosphere is a chemically inert atmosphere. The inert gas atmosphere may be specifically an atmosphere formed by an inert gas, and the inert gas may be, for example, one or two or more of nitrogen and a group zero gas (e.g., helium, argon). Preferably, it is carried out in a nitrogen atmosphere.

In the present invention, the feedstock for the fluidized processing of heavy oil may be a respective fluidized feedstock of heavy oil conventional in the art, such as atmospheric residue, vacuum residue, wax oil, and the like.

The present invention will be described in detail below by way of examples.

(1) The properties of the heavy oil fluidized feedstock used in the following examples of the present invention are shown in table 1. In the present invention, the contact agent to be fluidized with the heavy oil may be any of various contact agents conventionally used in the fluidized processing of heavy oil in the art. The contact agent comprises a catalytically active silicoaluminophosphate material contact agent, for example, may be a silicoaluminophosphate material containing greater than 50% by weight, including, but not limited to, one or more of molecular sieves, kaolin, alumina, amorphous silicoaluminophosphates, montmorillonite, quartz sand, and clay. Wherein, the molecular sieve can be a conventional molecular sieve, for example, X-type molecular sieve, Y-type molecular sieve, MCM series molecular sieve, etc.; in addition, the contact agent may also include inert material contact agents such as coke particles, quartz sand, and the like. The properties of a representative fluidized reaction contact agent used in the following examples of the present invention are shown in table 2.

(2) In the examples of the invention described below, the viscosity is determined by means of the standard petroleum asphalt kinematic viscometry of the petrochemical industry (SH/T0654-1998) using a HAAKE VT550 viscometer of the company HAAKE.

The viscosity reduction rate of the heavy oil is calculated by the following formula:

f＝(η₁-η₂)/η₁×100％

f-viscosity reduction ratio%

η₁Initial viscosity of heavy oil, mm²/s

η₂Viscosity, mm after addition of pretreatment agent²/s

(3) Taking a small fixed fluidized bed reactor as an example, the effect of the contact cracking reaction of the heavy oil after pretreatment is studied. After the reaction is finished, the coking rates of the heavy oil treated by various pretreatment agents are respectively compared with the coking rates of the heavy oil which is not treated by the treatment agents. The cracking reaction process conditions are as follows: the reaction temperature is 500 ℃, and the space velocity is 8h^-1Steam to heavy oil mass ratio of 1:3.75, contact agent to heavy oil mass ratio of 10:1, gas phase residence time of 0.8s, the same cracking reaction process conditions were used for each example and comparative example.

(4) The compounds used in the following examples and comparative examples of the present invention are all commercially available.

TABLE 1 Properties of the raw materials

TABLE 2 Main composition and Properties of the contact agent