阅读说明：本技术 确定用于脱除重油中镍的添加剂分子结构的方法、脱除重油中镍的添加剂 (Method for determining molecular structure of additive for removing nickel in heavy oil and additive for removing nickel in heavy oil ) 是由 任强 赵晓光 赵毅 王丽新 王春璐 叶蔚甄 曲亚坤 代振宇 周涵 于 2019-08-23 设计创作，主要内容包括：本发明提出了一种确定用于脱除重油中镍的添加剂分子结构的方法、脱除重油中镍的添加剂、脱除重油中镍的方法以及一种机器可读存储介质。本发明的确定用于脱除重油中镍的添加剂分子结构的方法,包括：获取用于脱除重油中镍的添加剂分子结构；计算该添加剂分子结构的Connolly表面积A；计算该添加剂分子结构的Chi指数χ；计算该添加剂分子结构的偶极矩μ；判断所述添加剂分子结构的Connolly表面积A、Chi指数χ、偶极矩μ是否在各自的预定范围内；在所述添加剂分子结构的Connolly表面积A、Chi指数χ、偶极矩μ在各自的预定范围内的情况下,确定所述添加剂分子结构能够用于脱除重油中的镍。本发明方法通过采用上述添加剂,可以脱除重油中的镍,计算结果快速准确。(The invention provides a method for determining the molecular structure of an additive for removing nickel in heavy oil, the additive for removing the nickel in the heavy oil, a method for removing the nickel in the heavy oil and a machine-readable storage medium. The invention discloses a method for determining the molecular structure of an additive for removing nickel in heavy oil, which comprises the following steps: obtaining an additive molecular structure for removing nickel in heavy oil; calculating the Connolly surface area A of the molecular structure of the additive; calculating Chi index Chi of the molecular structure of the additive; calculating the dipole moment mu of the molecular structure of the additive; judging whether the Connolly surface area A, Chi index χ and dipole moment μ of the molecular structure of the additive are in respective predetermined ranges; determining that the molecular structure of the additive can be used for removing nickel in heavy oil under the condition that the Connolly surface area A, Chi index chi and the dipole moment mu of the molecular structure of the additive are in respective predetermined ranges. The method can remove nickel in the heavy oil by adopting the additive, and the calculation result is quick and accurate.)

1. A method for determining the molecular structure of an additive for removing nickel from heavy oil, the method comprising:

obtaining an additive molecular structure for removing nickel in heavy oil;

calculating the Connolly surface area A of the molecular structure of the additive;

calculating Chi index Chi of the molecular structure of the additive;

calculating the dipole moment mu of the molecular structure of the additive;

judging whether the Connolly surface area A, Chi index χ and dipole moment μ of the molecular structure of the additive are in respective predetermined ranges;

in the case where the Connolly surface area A, Chi index χ, dipole moment μ of the molecular structure of the additive are within respective predetermined ranges, it is determined that the additive can be used for removing nickel from heavy oil.

2. The method of claim 1, wherein the molecular structure of the additive for removing nickel from heavy oil is obtained by a method of selecting a molecule of known structure or by a method of molecular design.

3. The method according to claim 1, characterized in that the Connolly surface area a of the molecular structure of the additive is calculated by quantum chemical means; calculating Chi index Chi of the molecular structure of the additive by a thermodynamic method; the dipole moment mu of the molecular structure of the additive was calculated by quantum chemical methods.

4. The method of claim 1, wherein the predetermined range of Connolly surface area a is(preferred is) (ii) a The predetermined range of the Chi index x is 25-30 (preferably 26-29); the predetermined range of the dipole moment mu is 0.1 to 0.6debye (preferably 0.15 to 0.5 debye).

5. A process according to claim 1, wherein the additive is an organic compound (preferably an aromatic organic compound, more preferably a polyalkyl-substituted polycyclic aromatic hydrocarbon).

6. The method according to claim 5, wherein the polycyclic aromatic hydrocarbon is naphthalene, anthracene or phenanthrene, and the polyalkyl substitution is performed by providing a plurality of alkyl substituents having a carbon number of C of 3 to 10 (preferably 4 to 6) on the polycyclic aromatic hydrocarbon, wherein the number of the substituents is 3 to 10₁～C₁₀(preferably C)₃～C₆)。

7. Removing heavy oilAn additive of nickel, the molecular structure of the additive satisfying the following conditions: the Connolly surface area A of the molecular structure of the additive is located at(preferably, it isMore preferably) (ii) a The Chi index Chi of the molecular structure of the additive is 25-30 (preferably 26-29, and more preferably 27-28); the dipole moment mu of the molecular structure of the additive is 0.1-0.6 debye (preferably 0.15-0.5 debye, more preferably 0.2-0.4 debye).

8. Additive according to claim 7, wherein the additive is an organic compound (preferably an aromatic organic compound, more preferably a polyalkyl-substituted polycyclic aromatic hydrocarbon).

9. The additive according to claim 8, wherein the polycyclic aromatic hydrocarbon is naphthalene, anthracene or phenanthrene, and the polyalkyl substitution means that a plurality of alkyl substituents are present on the polycyclic aromatic hydrocarbon, the number of substituents is 3 to 10 (preferably 4 to 6), and the carbon number of the alkyl group is C₁～C₁₀(preferably C)₃～C₆)。

10. A method for removing nickel from heavy oil, the method comprising: adding to a heavy oil an additive as defined in any one of claims 1 to 6 or an additive according to any one of claims 7 to 9.

11. The method of claim 10, wherein the nickel in the heavy oil is removed in a demetallization tower at a temperature of 300 to 500 ℃.

12. The method of claim 10 wherein said additive is added in an amount of 0.001% to 1% (preferably 0.01% to 0.1%) by mass of said heavy oil.

13. A machine-readable storage medium having stored thereon instructions for causing a machine to perform the method for determining the molecular structure of an additive for removing nickel from heavy oil of any one of claims 1 to 6.

Technical Field

The invention relates to a method for removing metals in heavy oil, in particular to a method for removing nickel in heavy oil.

Background

Among numerous metal elements in heavy oil, nickel, vanadium, iron, sodium, calcium, copper and arsenic all cause catalyst poisoning, and compared with other metal elements, nickel and vanadium mostly exist in colloid and asphaltene in the form of porphyrin and non-porphyrin organic complexes, and are difficult to remove by a common method. In the catalytic cracking process, the metallic nickel generated in the reaction process has extremely strong dehydrogenation capacity, and is deposited on the catalyst to increase the generation amount of gas and coke. And oily polycyclic aromatic hydrocarbon polymer or coke is generated after partial catalytic feeding and cracking products are dehydrogenated, so that the liquid yield is reduced, and the metal nickel porphyrin compound has great influence on the selectivity of the catalyst. In the process of burning and regenerating the catalyst, the metal Ni adsorbed on the catalyst can generate oxidation reaction under high temperature condition to generate NiO (melting point 1990 ℃), the NiO can be deposited on the surface of the catalyst to block the pore channel of the catalyst, and the contact between the raw oil and the active center of the catalyst is prevented in the subsequent reaction. In the heavy oil hydrotreating process, because the demetallization reaction is relatively easy to carry out, the generated metal is deposited on the surface of the catalyst in a sulfide form, and serious adverse effects are brought to the hydrogenation catalysis. It is reported that the service life of the hydrogenation catalyst is closely related to the nickel and vanadium content in the raw oil. Therefore, the harm of nickel and vanadium to the catalyst is particularly remarkable.

At present, the techniques for removing nickel from hydrocarbon oil mainly include the following types:

1) physical method

Because nickel compounds are mainly present in colloids and asphaltenes, asphaltene is usually removed by physical means such as solvent extraction and filtration, thereby removing metallic nickel. Patent CN 101218326a discloses a process for the upgrading and demetallization of heavy oils and bitumens by solvent deasphalting of the heavy and residual oils into lower boiling hydrocarbons with a greatly reduced metal content. Patent CN 1323339a uses solvent deasphalting to upgrade and desulfurize heavy hydrocarbon feeds containing sulfur, metals and asphaltenes. Patents US 5,192,421, CN 1344782A, CN 1117071A, CN 101068908A, CN 1844325a are also related. However, this process removes a large amount of convertible raw materials at the same time as the removal of pitch and metal species and requires the consumption of a large amount of solvent.

In addition, there are also patents for deasphalting by filtration, for example patent US4,411,790, which describes a process for ultrafiltration of vacuum residues at high temperature (330 ℃) by means of ceramic membranes having an average pore size of 10nm, so that the asphaltene content of the heavy oil is reduced from 6.3% to 4.1% and the vanadium content is reduced from 195ppm to 90 ppm. Patent US4,797,200 dilutes heavy oil with a solvent such as toluene and feeds the diluted oil to an ultrafiltration membrane filtration unit. The filtering membrane adopting the technology is easy to form a colloid layer by scaling, and has small treatment capacity, so the industrial application is difficult.

The patent CN 1140610C, CN 1356376A, CN 103374385A, CN 103374385B, CN 103374414A, CN 103374414B, CN 103374415A, CN 103374415B uses a chemical reagent to perform demetallization, and the operation process is complex and the cost is high.

2) Chemical process

The metal can also be removed by chemical reaction between the agent and the metallic nickel compound to destroy the structure. Patent US4,039,432 describes a method for removing nickel and vanadium from crude oil by using an aqueous solution of ferric trichloride or stannic chloride. Patent US4,460,458 describes a method for removing metals such as nickel, vanadium and the like from crude oil by using fluorinated sulfonic acid polymers. Patent US4,465,589 describes a method for removing harmful metals, sulfur and nitrogen from crude oil by using methylating agent, after reaction, adding acid gas aqueous solution to wash nickel and vanadium precipitate into water phase. Patent US4,645,589 describes a process for removing nickel and vanadium from crude oil by means of countercurrent extraction with phosphorus-containing compounds. In patent CN 1356376A, phosphorus-containing organic matter is added as a demetallization agent in the electric desalting process, and the total removal rate of nickel and vanadium can reach 70%. Patent US 6,007,705 describes a process for removing metals from hydrocarbon oils by the combined action of a strong alkaline aqueous solution, an oxygen-containing gas and a phase transfer agent. Although the chemical method has a certain effect of removing nickel and vanadium in the raw oil, the problems that the nickel and vanadium removal is difficult to overcome, such as large dosage of the nickel and vanadium removal agent, large consumption and high cost are caused; the requirement on equipment materials is high; other negative effects on downstream processing, etc., and thus industrial applications are greatly limited.

3) Hydroprocessing

The technology adopts a Hydrogenation Demetalization (HDM) catalyst to ensure that nickel and vanadium compounds are subjected to hydrogenation decomposition and accumulated in catalyst pores to form deposits, finally, catalyst pore channels are blocked to be inactivated, and the metal is removed by sacrificing the catalyst. Patent US 5,358,634 deals with an atmospheric residue containing 4.2 wt% of sulfur, 104ppm of vanadium and 32ppm of nickel in the presence of hydrogen with an activated carbon catalyst, which is reacted at 400 c in the presence of hydrogen, and which hydrogenation process is usually capable of removing at least 23% of the metals Ni and V, and the sulfur and carbon residue content is also greatly reduced. The catalyst invented in patent CN 1218086A can make heavy oil undergo hydrodemetallization and hydrodesulfurization simultaneously. Patents such as US4,585,546, US4,988,434, FR 2542754, CN 1609176a are also related. The technology has the disadvantages of large investment for equipment, fast deactivation of HDM catalyst, difficult regeneration and difficult treatment of waste catalyst.

Disclosure of Invention

The invention provides a method for determining the molecular structure of an additive for removing nickel in heavy oil, the additive for removing the nickel in the heavy oil, a method for removing the nickel in the heavy oil and a machine-readable storage medium.

In a first aspect, the present invention provides a method for determining the molecular structure of an additive for removing nickel from heavy oil, the method comprising:

obtaining an additive molecular structure for removing nickel in heavy oil;

calculating the Connolly surface area A of the molecular structure of the additive;

calculating Chi index Chi of the molecular structure of the additive;

calculating the dipole moment mu of the molecular structure of the additive;

judging whether the Connolly surface area A, Chi index χ and dipole moment μ of the molecular structure of the additive are in respective predetermined ranges;

in the case where the Connolly surface area A, Chi index χ, dipole moment μ of the molecular structure of the additive are within respective predetermined ranges, it is determined that the additive can be used for removing nickel from heavy oil.

According to the present invention, generally, nickel in the heavy oil includes metallic nickel, nickel oxide, and organic compounds of nickel.

According to the present invention, the molecular structure of the additive for removing nickel from heavy oil can be alternatively obtained by a method of selecting molecules of known structures or by a method of molecular design.

According to the invention, optionally, the Connolly surface area a of the molecular structure of the additive is calculated by means of quantum chemistry; calculating Chi index Chi of the molecular structure of the additive by a thermodynamic method; the dipole moment mu of the molecular structure of the additive was calculated by quantum chemical methods.

According to the invention, optionally, the predetermined range of the Connolly surface area a isPreferably, it isMore preferablyThe predetermined range of the Chi index Chi is 25-30, preferably 26-29, and more preferably 27-28; a pre-determined dipole moment muThe range is 0.1 to 0.6debye, preferably 0.15 to 0.5debye, and more preferably 0.2 to 0.4 debye.

According to the invention, optionally, the additive is an organic compound, preferably an aromatic organic compound, more preferably a polyalkyl-substituted polycyclic aromatic hydrocarbon. The polycyclic aromatic hydrocarbon can be naphthalene, anthracene or phenanthrene, the polyalkyl substitution means that a plurality of alkyl substituents exist on the polycyclic aromatic hydrocarbon, the number of the substituents is preferably 3-10, more preferably 4-6, and the carbon number of the alkyl is preferably C₁～C₁₀More preferably C₃～C₆。

In a second aspect, the present invention provides an additive for removing nickel from heavy oil, wherein the molecular structure of the additive satisfies the following conditions: the Connolly surface area A of the molecular structure of the additive is located atPreferably, it isMore preferablyThe Chi index Chi of the molecular structure of the additive is 25-30, preferably 26-29, and more preferably 27-28; the dipole moment mu of the molecular structure of the additive is 0.1-0.6 debye, preferably 0.15-0.5 debye, and more preferably 0.2-0.4 debye.

According to the invention, optionally, the additive is an organic compound, preferably an aromatic organic compound, more preferably a polyalkyl-substituted polycyclic aromatic hydrocarbon. The polycyclic aromatic hydrocarbon can be naphthalene, anthracene or phenanthrene, the polyalkyl substitution means that a plurality of alkyl substituents exist on the polycyclic aromatic hydrocarbon, the number of the substituents is preferably 3-10, more preferably 4-6, and the carbon number of the alkyl is preferably C₁～C₁₀More preferably C₃～C₆。

In a third aspect, the present invention provides a method for removing nickel from heavy oil, comprising: the above additives are added to the heavy oil.

According to the invention, the nickel in the heavy oil is removed in the demetallization tower at the temperature of 300-500 ℃.

According to the invention, the additive is optionally added in an amount of 0.001% to 1%, preferably 0.01% to 0.1%, by mass of the heavy oil.

In a fourth aspect, the present disclosure is directed to a machine-readable storage medium having instructions stored thereon for causing a machine to perform the method for determining the molecular structure of an additive for removing nickel from heavy oil as described above.

Through the technical scheme, the following beneficial effects can be realized:

1) by using the additive, nickel in the heavy oil can be removed.

2) Compared with the traditional experimental method, the method for determining the molecular structure of the additive for removing the nickel in the heavy oil can enable the calculation result to be fast and accurate, reduce a large number of experiments and save labor cost and experiment cost.

The features and advantages of the present invention will be described in detail in the detailed description that follows.

Drawings

Fig. 1 is a flow chart of a method for determining the molecular structure of an additive for removing nickel from heavy oil according to an embodiment of the present invention.

The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the embodiments of the invention without limiting the embodiments of the invention.

Detailed Description

The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration and explanation only, not limitation.

One embodiment of the present invention provides an additive for removing nickel from heavy oil, wherein the molecular structure of the additive satisfies the following conditions:

the additive is prepared byThe Connolly surface area A of the molecular structure is in

The Chi index Chi of the molecular structure of the additive is 25-30;

the dipole moment mu of the molecular structure of the additive is 0.1-0.6 debye.

Nickel in heavy oil is removed in a demetallization tower by adding an additive having a molecular structure satisfying the above conditions to the heavy oil and heating to 450 ℃.

Table 1 below shows the removal effect of nickel from heavy oil after additives with different molecular structures are added into heavy oil according to different amounts, and the removal rate of nickel can be determined by detecting the nickel content in heavy oil before and after removal. The nickel content is determined by standard prior art methods of measuring the nickel content of metals.

TABLE 1 Denickelling Effect of different additives on heavy oils

Fig. 1 is a flow chart of a method for determining the molecular structure of an additive for removing nickel from heavy oil according to an embodiment of the present invention. As shown in fig. 1, an embodiment of the present invention provides a method for determining a molecular structure of an additive for removing nickel from heavy oil, the method including:

and step S110, acquiring an additive molecular structure for removing nickel in the heavy oil.

In step S120, the Connolly surface area A of the molecular structure of the additive is calculated. The Connolly surface area a of the molecular structure of the additive can be calculated using methods known in the art.

Step S130, calculating Chi index Chi of the molecular structure of the additive. The Chi index χ of the molecular structure of the additive can be calculated using methods known in the art.

In step S140, the dipole moment μ of the molecular structure of the additive is calculated. The dipole moment μ of the molecular structure of the additive can be calculated using methods well known in the art.

Step S150, judging whether the Connolly surface area A, Chi index χ and dipole moment μ of the molecular structure of the additive are in respective preset ranges; and (3) under the condition that the Connolly surface area A, Chi index χ and the dipole moment μ of the additive molecular structure are in respective preset ranges, performing the following step S160, otherwise, re-acquiring the additive molecular structure for removing the nickel in the heavy oil, and continuing to perform the steps S120-S150 until the additive molecular structure with the Connolly surface area A, Chi index χ and the dipole moment μ in respective preset ranges is found.

And step S160, determining that the molecular structure of the additive can be used for removing nickel in heavy oil.

Optionally, the Connolly surface area A of the molecular structure of the additive is atPreferably, it isMore preferablyThe Chi index Chi of the molecular structure of the additive is 25-30, preferably 26-29, and more preferably 27-28; the dipole moment mu of the molecular structure of the additive is 0.1-0.6 debye, preferably 0.15-0.5 debye, and more preferably 0.2-0.4 debye. Compared with the traditional experimental method, the method for determining the molecular structure of the additive for removing the nickel in the heavy oil can enable the calculation result to be fast and accurate, reduce a large number of experiments and save labor cost and experiment cost.

Although the embodiments of the present invention have been described in detail with reference to the accompanying drawings, the embodiments of the present invention are not limited to the details of the above embodiments, and various simple modifications can be made to the technical solutions of the embodiments of the present invention within the technical idea of the embodiments of the present invention, and the simple modifications all belong to the protection scope of the embodiments of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, the embodiments of the present invention do not describe every possible combination.

Those skilled in the art will understand that all or part of the steps in the method according to the above embodiments may be implemented by a program, which is stored in a storage medium and includes several instructions to enable a single chip, a chip, or a processor (processor) to execute all or part of the steps in the method according to the embodiments of the present application. And the aforementioned storage medium includes: a U-disk, a removable hard disk, a Read-Only Memory (ROM), a Random Access Memory (RAM), a magnetic disk or an optical disk, and other various media capable of storing program codes.