Deashing agent for alkali-catalyzed slurry oil and its application, and method for removing solid particles in slurry oil

Abstract

This invention relates to petroleum refining technology, and discloses a deashing agent for alkali-catalyzed oil slurry systems, its application, and a method for removing solid particles from the oil slurry. The deashing agent contains a charge neutralizer, a demulsifier, a dimer acid polyamide, and a solvent; wherein, by weight percentage, the charge neutralizer contains 2-10%, the demulsifier contains 2-15%, the dimer acid polyamide contains 10-40%, and the balance is solvent. The method for removing solid particles from the oil slurry includes the following steps: mixing the deashing agent with an oil slurry containing an alkaline catalyst and then subjecting it to sedimentation treatment. This deashing agent can remove alkaline catalyst powder from the oil slurry and significantly improves the removal efficiency.

Description

Technical Field

[0001] This invention relates to petroleum refining and processing technology, specifically to a deashing agent for alkali-catalyzed oil slurry and its application, and a method for removing solid particles from the oil slurry. Background Technology

[0002] Using catalytic cracking external oil slurry for deconsolidation treatment in the production of high-end carbon materials such as carbon black and needle coke has become an important development direction for refining and chemical enterprises. Chemical oil slurry deconsolidation technology based on oil slurry deashing agents (also known as oil slurry settling agents or oil slurry deconsolidating agents) is currently the main method for oil slurry deconsolidation due to its low cost and stable effect.

[0003] Chinese patent application CN115216331A reports a polyalkyl branched phenolic resin type deashing agent for oil slurry. This settling agent uses melamine-modified polyalkyl branched phenolic resin as the main agent, which destroys the spatial network structure formed by the self-association of asphaltene, thereby removing 98% of the ash from the oil slurry within 4-8 hours. Chinese patent application CN113322095A synthesizes an amine-modified phenolic resin as an oil slurry deashing agent. This structure has a high decomposition temperature and is suitable for oil slurry treatment in high-temperature environments. Chinese patent application CN106928058B synthesizes a formaldehyde condensate polymer of alkylphenol polyoxyethylene ether ester, which can promote the sedimentation of solid particles in oil slurry without the need for compounding with other additives. Chinese patent application CN107849465A uses poly(meth)acrylic acid resin, alkyl quaternary ammonium salt, alkyl(oxy)phenolic resin and solvent to form an oil slurry deashing agent. It has a small dosage, simple operation, and does not contain sulfur, halogens, heavy metals and other elements that are harmful to the environment. While the aforementioned deashing agents for slurry oil are highly effective, they are only suitable for external slurry oil discharge from traditional catalytic cracking units. With the development of crude oil-to-chemicals technology, traditional catalytic cracking units are replacing or partially incorporating alkaline catalysts with acidic catalysts to increase the yield of low-carbon olefins. This change in catalyst type renders the original deashing agents ineffective.

[0004] Therefore, there is an urgent need to develop a deashing agent suitable for alkali-catalyzed oil slurry systems to meet the deep processing requirements of oil slurry under new technologies. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems existing in the prior art and provide a deashing agent for alkali catalytic system slurry, as well as its application and method. This deashing agent can remove alkaline catalyst powder from alkali catalytic system slurry and significantly improves the removal effect of the deashing agent.

[0006] The first aspect of the present invention provides a deashing agent for slurry oil in an alkaline catalytic system, the deashing agent comprising a charge neutralizer, a demulsifier, a dimer acid polyamide and a solvent; wherein, by weight percentage, the charge neutralizer comprises 2-10%, the demulsifier comprises 2-15%, the dimer acid polyamide comprises 10-40%, and the balance is a solvent.

[0007] Preferably, by weight percentage, the charge neutralizer contains 5-8%, the demulsifier contains 8-12%, and the dimer acid polyamide contains 25-35%.

[0008] Preferably, the dimer acid polyamide is a polycondensation product of an aliphatic diacid and a polyamine.

[0009] Preferably, the aliphatic dicarboxylic acid is selected from at least one of C8-C44 straight-chain dicarboxylic acids, diundecenoic acid, diolithoic acid, ditetradecenoic acid, dipalmitoic acid, dioleoic acid, dilinoleic acid, dilinolenic acid, diricinoleic acid, diarachidonic acid, and didocoshexaenoic acid; and the polyamine is selected from at least one of C2-C18 aliphatic diamines, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptaamine, phenylenediamine, and cyclohexanediamine.

[0010] Preferably, the dimer acid polyamide is a condensation product of dimer oleic acid and octadecanediamine, a condensation product of dodecanoic acid and phenylenediamine, or a condensation product of dimer palmitic acid and triethylenetetramine.

[0011] Preferably, the molecular weight of the dimer acid polyamide is 1000-10000, more preferably 3000-5000.

[0012] Preferably, the charge neutralizer contains aliphatic amine polyoxyethylene ether.

[0013] Preferably, in the fatty amine polyoxyethylene ether, the alkyl group in the fatty amine is C8-C24 alkyl, more preferably C12-C18 alkyl; the number of repeating units in the polyoxyethylene ether is 2-30, more preferably 10-18.

[0014] Preferably, the demulsifier contains alkylphenol resin polyoxyethylene polyoxypropylene ether.

[0015] Preferably, the alkylphenol resin polyoxyethylene polyoxypropylene ether is the product of a contact reaction between alkylphenol resin, propylene oxide, and ethylene oxide.

[0016] Preferably, the molecular weight of the alkylphenol resin is 3,000-20,000, and more preferably 8,000-12,000.

[0017] Preferably, in the alkylphenol resin, the alkyl group is C4-C18, and more preferably C8-C12 alkyl.

[0018] Preferably, the molar ratio of propylene oxide to ethylene oxide is 0.5-10:1, and more preferably 3-6:1.

[0019] Preferably, the solvent contains an aromatic solvent oil.

[0020] Preferably, the aromatic solvent oil has a flash point higher than 60°C.

[0021] Preferably, the solvent further contains a co-solvent.

[0022] Preferably, the co-solvent contains 5-20% by weight, more preferably 10-15%.

[0023] Preferably, the co-solvent is selected from at least one of ethylene glycol diethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, ethylene glycol ethyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether.

[0024] A second aspect of the present invention provides the application of the deashing agent described in the first aspect in an oil slurry containing an alkaline catalyst.

[0025] Preferably, the slurry also contains an acidic catalyst.

[0026] The third aspect of the present invention provides a method for removing solid particles from oil slurry, comprising the following steps: mixing the deashing agent described in the first aspect with oil slurry containing an alkaline catalyst and then performing sedimentation treatment.

[0027] Preferably, the conditions for the sedimentation treatment include at least: a temperature of 80-130℃ and a time of 12-72h.

[0028] Preferably, the weight ratio of the deashing agent to the alkaline catalyst is 0.05-0.1:1.

[0029] The beneficial effects of the present invention through the above technical solution are as follows:

[0030] The deashing agent for alkali-catalyzed oil slurry provided by this invention contains a charge neutralizer, a demulsifier, a dimer acid polyamide, and a solvent. Through the interaction between the charge neutralizer, demulsifier, and dimer acid polyamide, it improves the removal efficiency of alkaline catalyst powder from the oil slurry under alkali catalysis. Specifically, the charge neutralizer eliminates the static charge on the surface of the alkaline catalyst, the demulsifier eliminates the emulsification effect of the asphalt in the oil slurry, and the dimer acid polyamide promotes the removal of alkaline catalyst powder from the oil slurry under alkali catalysis, significantly improving the deashing rate. Furthermore, this deashing agent has good applicability, significant effect, and good compatibility with other additives, showing promising prospects for industrial application. Detailed Implementation

[0031] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0032] The first aspect of the present invention provides a deashing agent for slurry oil in an alkaline catalytic system, the deashing agent comprising a charge neutralizer, a demulsifier, a dimer acid polyamide and a solvent; wherein, by weight percentage, the charge neutralizer comprises 2-10%, the demulsifier comprises 2-15%, the dimer acid polyamide comprises 10-40%, and the balance is a solvent.

[0033] During their research, the inventors discovered that the deashing agent, containing a charge neutralizer, a demulsifier, a dimer acid polyamide, and a solvent, can improve the removal efficiency of alkaline catalyst powder from oil slurry under alkaline catalysis through the interaction between the charge neutralizer, demulsifier, and dimer acid polyamide. Specifically, the charge neutralizer eliminates the static charge on the surface of the alkaline catalyst, the demulsifier eliminates the emulsification of asphalt in the oil slurry, and the dimer acid polyamide promotes the removal of alkaline catalyst from the oil slurry under alkaline catalysis, significantly improving the deashing rate. Furthermore, this deashing agent exhibits good applicability, significant effects, and good compatibility with other additives, showing promising prospects for industrial application.

[0034] According to the present invention, preferably, the charge neutralizer contains 5-8% by weight, the demulsifier contains 8-12%, and the dimer acid polyamide contains 25-35%. The inventors have found that, under this preferred embodiment, the interaction between the charge neutralizer, the demulsifier, and the dimer acid polyamide is further enhanced, thereby increasing the deashing rate of the deashing agent.

[0035] According to the present invention, preferably, the dimer acid polyamide is a condensation product of an aliphatic diacid and a polyamine. The inventors have discovered that, under the action of this particularly preferred embodiment, the dimer acid polyamide can promote the removal of alkaline catalyst powder from the slurry oil in the alkaline catalytic system.

[0036] According to the present invention, in order to further improve the removal effect of the deashing agent on the alkaline catalyst in the slurry of the alkaline catalytic system, preferably, the aliphatic dicarboxylic acid is selected from at least one of C8-C44 straight-chain dicarboxylic acids, diundecenoic acid, diolithoic acid, ditetradecenoic acid, dipalmitoic acid, dioleoic acid, dilinoleic acid, dilinolenic acid, diricinoleic acid, diarachidonic acid, and didocoshexaenoic acid; and the polyamine is selected from at least one of C2-C18 aliphatic diamines, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptaamine, phenylenediamine, and cyclohexanediamine.

[0037] According to the present invention, in order to further improve the removal effect of the deashing agent on the alkaline catalyst in the slurry of the alkaline catalytic system, preferably, the dimer acid polyamide is a condensation product of dimer oleic acid and octadecanediamine, a condensation product of dodecanediic acid and phenylenediamine, or a condensation product of dimer palmitic acid and triethylenetetramine.

[0038] According to the present invention, in order to further improve the removal effect of the deashing agent on the alkaline catalyst in the slurry of the alkaline catalytic system, preferably, the molecular weight of the dimer acid polyamide is 1000-10000, and more preferably 3000-5000.

[0039] According to the present invention, preferably, the charge neutralizing agent contains aliphatic amine polyoxyethylene ether. The inventors have found that, under this preferred embodiment, the aliphatic amine polyoxyethylene ether has good charge neutralizing ability, effectively eliminating the static charge on the surface of the alkaline catalyst, thereby improving the antistatic effect of the deashing agent and its removal effect on the alkaline catalyst in the oil slurry.

[0040] According to the present invention, in order to further eliminate the static charge on the surface of the alkaline catalyst, preferably, in the aliphatic amine polyoxyethylene ether, the alkyl group in the aliphatic amine is C8-C24 alkyl, more preferably C12-C18 alkyl; the number of repeating units in the polyoxyethylene ether is 2-30, more preferably 10-18.

[0041] In this invention, in aliphatic amine polyoxyethylene ether, the number of repeating units of polyoxyethylene ether refers to the number of times -CH2-CH2-O- is repeated.

[0042] According to the present invention, preferably, the demulsifier contains alkylphenol resin polyoxyethylene polyoxypropylene ether. The inventors have found that, under this preferred embodiment, alkylphenol resin polyoxyethylene polyoxypropylene ether can eliminate the emulsification of gum asphalt in the oil slurry, thereby improving the removal effect of the deashing agent on the alkaline catalyst in the oil slurry.

[0043] According to the present invention, in order to further improve the removal effect of the deashing agent on alkaline catalysts in oil slurry, preferably, the alkylphenol resin polyoxyethylene polyoxypropylene ether is the product of a contact reaction of alkylphenol resin, propylene oxide, and ethylene oxide. More preferably, the contact reaction process includes: using alkylphenol resin as an initiator, sequentially initiating propylene oxide and ethylene oxide to obtain alkylphenol resin polyoxyethylene polyoxypropylene ether.

[0044] For example, the contact reaction process includes: using alkylphenol resin as an initiator and alkali as a catalyst, under reaction conditions of 125-150℃ and 0.1-0.8MPa, propylene oxide is introduced to carry out a polymerization reaction. After the pressure inside the reactor is zero, ethylene oxide is introduced to carry out a polymerization reaction. After the pressure inside the reactor is zero, the polymerization reaction ends, and the product is discharged after dehydration to obtain alkylphenol resin polyoxyethylene polyoxypropylene ether.

[0045] According to the present invention, in order to further eliminate the emulsifying effect of the asphalt in the slurry, preferably, the molecular weight of the alkylphenol resin is 3000-20000, more preferably 8000-12000.

[0046] According to the present invention, in order to further eliminate the emulsifying effect of the asphalt in the slurry, preferably, the alkyl group in the alkylphenol resin is C4-C18, more preferably C8-C12. Wherein, the alkyl chain length refers to the carbon chain length of the alkyl group.

[0047] According to the present invention, in order to further eliminate the emulsifying effect of the asphalt resin in the slurry, preferably, the molar ratio of propylene oxide to ethylene oxide is 0.5-10:1, more preferably 3-6:1. It should be noted that the molar ratio of propylene oxide to ethylene oxide of 0.5-10:1 refers to the feeding molar ratio of propylene oxide to ethylene oxide being 0.5-10:1 during the contact reaction of alkylphenol resin, propylene oxide, and ethylene oxide.

[0048] In this invention, the molar ratio of alkylphenol resin to propylene oxide is 1:4-10.

[0049] In this invention, alkylphenol resin polyoxyethylene polyoxypropylene ether can be obtained commercially or prepared in-house.

[0050] According to the present invention, preferably, the solvent contains an aromatic solvent oil. The inventors have discovered that, under this preferred embodiment, dissolving the charge neutralizer, demulsifier, and dimer polyamide in the solvent can improve the removal effect of the deashing agent on solid particles in the oil slurry.

[0051] According to the present invention, in order to further improve the removal effect of the deashing agent on the alkaline catalyst in the oil slurry, preferably, the flash point of the aromatic solvent oil is higher than 60°C.

[0052] According to the present invention, in order to further improve the removal effect of the deashing agent on the alkaline catalyst in the oil slurry, preferably, the aromatic solvent oil is selected from at least one of 150# solvent oil, 180# solvent oil, 200# solvent oil and diphenyl ether.

[0053] According to the present invention, preferably, the solvent further contains a co-solvent. The inventors have found that, in this preferred embodiment, the addition of the co-solvent can improve the solubility of polar substances, thereby enhancing the removal effect of the deashing agent on alkaline catalysts in the oil slurry.

[0054] According to the present invention, in order to further improve the removal effect of the deashing agent on the alkaline catalyst in the oil slurry, preferably, the co-solvent contains 5-20% by weight, more preferably 10-15%.

[0055] According to the present invention, in order to further improve the removal effect of the deashing agent on alkaline catalysts in oil slurry, preferably, the co-solvent is selected from at least one of ethylene glycol diethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, ethylene glycol ethyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether, and further selected from at least one of dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monobutyl ether, and ethylene glycol butyl ether.

[0056] According to the present invention, all of the above-mentioned substances can be obtained commercially or prepared in-house.

[0057] According to a particularly preferred embodiment of the present invention, a deashing agent for an alkaline catalytic system slurry is provided, the deashing agent comprising a charge neutralizer, a demulsifier, a dimer acid polyamide, an aromatic solvent, and a co-solvent; by weight percentage, the charge neutralizer comprises 5-8%, the demulsifier comprises 8-12%, the dimer acid polyamide comprises 25-35%, the co-solvent comprises 10-15%, and the balance is an aromatic solvent oil;

[0058] The dimer acid polyamide is a condensation product of dimer oleic acid and octadecanediamine, a condensation product of dodecanediic acid and phenylenediamine, or a condensation product of dimer palmitic acid and triethylenetetramine, with a molecular weight of 3000-5000. The charge neutralizer contains aliphatic amine polyoxyethylene ether, wherein the alkyl group in the aliphatic amine is C12-C18, and the number of repeating units in the polyoxyethylene ether is 10-18. The demulsifier contains alkylphenol resin polyoxyethylene polyoxypropylene ether. The preparation process of alkylphenol resin polyoxyethylene polyoxypropylene ether includes: using alkylphenol resin as an initiator to initiate propylene oxide and ethylene oxide; the molecular weight of alkylphenol resin is 8000-12000, in which the alkyl group is C8-C12 alkyl, and the molar ratio of propylene oxide to ethylene oxide is 3-6:1; the flash point of the aromatic solvent oil is higher than 60℃, and the co-solvent is selected from at least one of dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monobutyl ether, and ethylene glycol butyl ether.

[0059] The preferred embodiment described above provides a deashing agent that effectively removes alkaline catalysts from oil slurry, significantly improving the deashing rate.

[0060] In this invention, the deashing agent for oil slurry can be prepared by mixing the raw materials in a conventional manner. Preferably, the preparation process includes: preheating the dimer acid polyamide to 40-60°C and then adding it to a reaction vessel; adding aromatic solvent oil and co-solvent; stirring at 40-60°C for 20-60 minutes to completely dissolve the dimer acid polyamide; then sequentially adding a charge neutralizer and a demulsifier; and stirring until the system is clear.

[0061] A second aspect of the present invention provides the application of the deashing agent described in the first aspect in an oil slurry containing an alkaline catalyst.

[0062] According to the present invention, when the slurry to be treated is an alkaline catalytic system slurry, a deashing agent can be added to the slurry to remove the alkaline catalyst, resulting in a high deashing rate.

[0063] In this invention, when the slurry to be treated is a mixed catalytic system (containing both alkaline and acidic catalysts), a deashing agent provided by this invention and a conventional slurry deashing agent can be added. The deashing agent provided by this invention is used to remove the alkaline catalyst, and the conventional slurry deashing agent is used to remove the acidic catalyst. Exemplarily, the deashing agent and the conventional slurry deashing agent are mixed and used together through two different injection ports, with the injection ratio being the same as the mass ratio of the two catalyst powders in the slurry.

[0064] In this invention, the deashing agent can achieve good deconsolidation effect on oil slurries in different alkaline catalytic systems, and has good applicability.

[0065] In this invention, the deashing agent exhibits good compatibility with other additives. For example, when the viscosity of the oil slurry to be treated is high and it is difficult to perform deconsolidation, the deashing agent can be used in conjunction with an amide-based oil slurry viscosity modifier to improve the oil slurry viscosity and remove alkaline catalysts, thereby enhancing the deashing agent's removal effect on alkaline catalysts.

[0066] The third aspect of the present invention provides a method for removing solid particles from oil slurry, comprising the following steps: mixing the deashing agent according to any one of claims 1 to 7 with oil slurry containing an alkaline catalyst and then performing sedimentation treatment.

[0067] According to the present invention, in order to further improve the removal effect of the deashing agent on alkaline catalysts in oil slurry, preferably, the sedimentation treatment conditions include at least: a temperature of 80-130°C and a time of 12-72h.

[0068] According to the present invention, in order to further improve the removal effect of the deashing agent on solids in oil slurry, preferably, the weight ratio of the deashing agent to the alkaline catalyst is 0.05-0.1:1.

[0069] The present invention will be described in detail below with reference to embodiments, but this does not limit the scope of the invention.

[0070] In the following examples and comparative examples, the following dimeric acid polyamides were obtained: dimeric oleic acid copolymerized with octadecanediamine (molecular weight 5000), dimeric acid polyamide copolymerized with dodecanediic acid and phenylenediamine (molecular weight 3000), dimeric acid polyamide copolymerized with palmitic acid and triethylenetetramine (molecular weight 4000), dimeric acid polyamide copolymerized with octanoic acid and ethylenediamine, and dimeric acid polyamide copolymerized with docosahexaenoic acid, cyclohexanediamine, and butanediamine (molecular weight 10000), all purchased from Tianjin Yusheng Chemical Co., Ltd.; dodecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 18), octadecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 10), hexadecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 14), tetradecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 30), and octylamine polyoxyethylene ether (polyoxyethylene repeating unit number 10). 2) All raw materials were purchased from Anyi Chemical Co., Ltd.; Octylphenol resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 8000, propylene oxide to ethylene oxide molar ratio 3:1), dodecylphenol resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 12000, propylene oxide to ethylene oxide molar ratio 6:1), nonylphenol resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 10000, propylene oxide to ethylene oxide molar ratio 4:1), octadecylphenol resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 20000, propylene oxide to ethylene oxide molar ratio 0.5:1), and tert-butylphenol resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 3000, propylene oxide to ethylene oxide molar ratio 10:1) were all purchased from Shenzhen Yoshida Chemical Co., Ltd.; the remaining raw materials were purchased commercially unless otherwise specified.

[0071] Example 1

[0072] Dimeric acid polyamide (molecular weight 5000) copolymerized with 35% wt% dimer oleic acid and octadecanediamine was preheated to 50°C and then added to a reactor. 37% wt% 200# solvent oil and 15% wt% dipropylene glycol dimethyl ether were added and stirred at 50°C for 50 min to completely dissolve the dimer acid polyamide. Then, 5% wt% dodecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 18) and 8% octylphenol resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 8000, propylene oxide to ethylene oxide molar ratio 3:1) were added sequentially and stirred until the system was clear to obtain a deashing agent.

[0073] Example 2

[0074] Dimeric acid polyamide (molecular weight 3000) copolymerized with 25% dodecanoic acid and phenylenediamine was preheated to 50°C and then added to a reaction vessel. 45% 150# solvent oil and 10% diethylene glycol were added and stirred at 50°C for 50 min to completely dissolve the dimeric acid polyamide. Then, 8% octadecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 10) and 12% dodecylphenol resin polyoxyethylene polyoxypropylene ether (phenol resin molecular weight 12000, propylene oxide to ethylene oxide molar ratio 6:1) were added sequentially and stirred until the system was clear to obtain a deashing agent.

[0075] Example 3

[0076] Dimeric acid polyamide (molecular weight 4000) copolymerized with 30% dimer palmitic acid and triethylenetetramine was preheated to 50°C and then added to a reactor. 42% wt% 180# solvent oil and 12% wt% diethylene glycol monobutyl ether were added and stirred at 50°C for 50 min to completely dissolve the dimer acid polyamide. Then, 6% wt% hexadecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 14) and 10% wt% nonylphenolic resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 10000, propylene oxide to ethylene oxide molar ratio 4:1) were added sequentially and stirred until the system was clear to obtain a deashing agent.

[0077] Example 4

[0078] Dimeric acid polyamide (molecular weight 5000) copolymerized from 10% dimer oleic acid and octadecanediamine was preheated to 50°C and then added to a reactor. 45% 200# solvent oil and 20% dipropylene glycol dimethyl ether were added and stirred at 50°C for 50 min to completely dissolve the dimer acid polyamide. Then, 10% dodecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 18) and 15% octylphenol resin polyoxyethylene polyoxypropylene ether (phenol resin molecular weight 8000, propylene oxide to ethylene oxide molar ratio 3:1) were added sequentially and stirred until the system was clear to obtain a deashing agent.

[0079] Example 5

[0080] The deashing agent was prepared according to the method of Example 1, except that the dimer acid polyamide (molecular weight 5000) copolymerized with dimer oleic acid and octadecanediamine was replaced with dimer acid polyamide (molecular weight 1000) copolymerized with octadiac acid and ethylenediamine.

[0081] Example 6

[0082] The deashing agent was prepared according to the method of Example 1, except that dodecylamine polyoxyethylene ether (polyoxyethylene repeating unit number of 18) was replaced with polydimethyldiallyl ammonium chloride (molecular weight of 30000).

[0083] Example 7

[0084] The deashing agent was prepared according to the method of Example 1, except that octylphenol resin polyoxyethylene polyoxypropylene ether (phenol resin molecular weight is 8000, and the molar ratio of propylene oxide to ethylene oxide is 3:1) was replaced with polyoxyethylene polyoxypropylene octadecyl alcohol ether (molecular weight is 8000, and the molar ratio of propylene oxide to ethylene oxide is 3:1).

[0085] Example 8

[0086] Dimeric acid polyamide (molecular weight 4000) copolymerized with 30% by weight of dimer palmitic acid and triethylenetetramine was preheated to 50°C and then added to a reaction vessel. 54% by weight of 180# solvent oil was added and stirred at 50°C for 50 min to completely dissolve the dimer acid polyamide. Then, 6% by weight of hexadecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 14) and 10% by weight of nonylphenolic resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 10000, propylene oxide to ethylene oxide molar ratio 4:1) were added sequentially and stirred until the system was clear to obtain a deashing agent.

[0087] Example 9

[0088] 10% by weight of dimeric acid polyamide (molecular weight 1000) copolymerized with octanoic acid and ethylenediamine was preheated to 50°C and then added to a reaction vessel. 65% by weight of diphenyl ether was added and stirred at 50°C for 50 min to completely dissolve the dimeric acid polyamide. Then, 10% by weight of tetratetraalkylamine polyoxyethylene ether (polyoxyethylene repeating unit number 30) and 15% by weight of octadecylphenol resin polyoxyethylene polyoxypropylene ether (phenol resin molecular weight 20000, propylene oxide to ethylene oxide molar ratio 0.5:1) were added sequentially and stirred until the system was clear to obtain a deashing agent.

[0089] Example 10

[0090] 40 wt% of a dimer acid polyamide (molecular weight 10000) copolymerized with cyclohexanediamine and butanediamine was preheated to 50°C and then added to a reactor. 36 wt% of 150# solvent oil and 20 wt% of ethylene glycol butyl ether were added and stirred at 50°C for 50 min to completely dissolve the dimer acid polyamide. Then, 2 wt% of octylamine polyoxyethylene ether (polyoxyethylene repeating unit number 2) and 2 wt% of tert-butylphenol resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 3000, propylene oxide to ethylene oxide molar ratio 10:1) were added sequentially and stirred until the system was clear to obtain a deashing agent.

[0091] Comparative Example 1

[0092] Dimeric acid polyamide (molecular weight 4000) copolymerized with 35% dimer palmitic acid and triethylenetetramine was preheated to 50°C and then added to a reaction vessel. 48% wt% 180# solvent oil and 12% wt% diethylene glycol monobutyl ether were added and stirred at 50°C for 50 min to completely dissolve the dimer acid polyamide. Then, 10% wt% nonylphenolic resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight 10000, propylene oxide to ethylene oxide molar ratio 4:1) was added and stirred until the system was clear to obtain a deashing agent.

[0093] Comparative Example 2

[0094] Dimeric acid polyamide (molecular weight 4000) copolymerized with 30% dimer palmitic acid and triethylenetetramine was preheated to 50°C and then added to a reaction vessel. 52% 180# solvent oil and 12% diethylene glycol monobutyl ether were added and stirred at 50°C for 50 min to completely dissolve the dimer acid polyamide. Then, 6% hexadecylamine polyoxyethylene ether (polyoxyethylene repeating unit number 14) was added and stirred until the system was clear to obtain a deashing agent.

[0095] Comparative Example 3

[0096] 6% by weight of hexadecylamine polyoxyethylene ether (polyoxyethylene repeating unit number of 14), 10% by weight of nonylphenolic resin polyoxyethylene polyoxypropylene ether (phenolic resin molecular weight of 10000, propylene oxide to ethylene oxide molar ratio of 4:1), 72% by weight of 180# solvent oil and 12% by weight of diethylene glycol monobutyl ether were added to a reaction vessel and stirred at 50°C until the system became clear to obtain a deashing agent.

[0097] Comparative Example 4

[0098] The deashing agent was prepared according to the method of Example 1, except that the dimer acid polyamide (molecular weight 5000) copolymerized with dimer oleic acid and octadecanediamine was replaced with polyoxyethylene polyoxypropylene block copolymer (molecular weight 8000, molar ratio of propylene oxide to ethylene oxide 4:1) to obtain the deashing agent.

[0099] Test Example 1

[0100] The deashing agents prepared in Examples 1-10 and Comparative Examples 1-4, as well as commercially available deashing agent X (purchased from Shenzhen Kelada Fine Chemical Co., Ltd., model CK2704A) and deashing agent Y (our own product, model TH-CJ01), were subjected to performance tests. The oil slurry to be tested was oil slurry A, which was obtained entirely using an alkaline catalyst device and had a kinematic viscosity of 28 mmHg. 2 / S (100℃), the content of resin and asphalt is 7.66%, and the content of ash (i.e. alkaline catalyst) is 0.24%.

[0101] The specific testing process includes: taking about 200g of oil slurry A and preheating it to 100℃, adding the above-mentioned deashing agent according to the designed amount, mechanically stirring and mixing evenly, and then letting it stand and settle at the set temperature. The upper layer of oil slurry is taken for testing at different times.

[0102] The deashing agents from Examples 1-10 and Comparative Examples 1-4, as well as deashing agents X and Y, were added to the oil slurry according to the amounts relative to oil slurry A in Table 1. The ash content in oil slurry A was determined according to the standard GB / T 508-85 Petroleum Products Ash Content Determination Method, the deashing rate was calculated, and a reference group (no deashing agent was added to the oil slurry) was set up. The results are shown in Table 1.

[0103] Table 1

[0104]

[0105]

[0106] As shown in Table 1, adding the deashing agents prepared in Examples 1-10 to oil slurry A can reduce the ash content in the oil slurry to below 0.05%, achieving a deashing rate of over 80%. Specifically, the deashing agents prepared in Examples 1-3 can achieve a deashing rate of 90%, while the deashing agents prepared in Comparative Examples 1-4, due to the lack of key raw material components, still have an ash content of over 0.2% in the treated oil slurry, making it difficult to meet subsequent production requirements. Similarly, currently commercially available deashing agents X and Y cannot effectively remove alkaline catalyst powder from the oil slurry.

[0107] Test Example 2

[0108] The deashing agent prepared in Example 3 (designated as deashing agent C), commercially available deashing agents X and Y, and amide-based slurry viscosity modifier Z (a proprietary product of our company, whose preparation method is described in Example 1 of application number ZL202011570944.4) were subjected to compatibility evaluation tests. The slurry to be tested was slurry B, which was obtained from a mixed catalytic system (20% by weight of alkaline catalyst and 80% by weight of acidic catalyst) with a kinematic viscosity of 50 mmHg. 2 / S (100℃), the content of resin and asphalt is 11.23%, and the ash content (i.e., a mixture of alkaline catalyst and acid catalyst, with the mass ratio of alkaline catalyst to acid catalyst being 1:4) is 0.34%.

[0109] The specific testing process includes: taking about 200g of oil slurry B and preheating it to 100℃, adding the above-mentioned deashing agent according to the design amount, mechanically stirring and mixing evenly, letting it stand and settle at 110℃ for 48h, and taking the upper layer of oil slurry for testing.

[0110] Deashing agent C, deashing agent X, deashing agent Y, and amide-based slurry viscosity modifier Z were added to the slurry according to the amounts shown in Table 2 relative to slurry B. The ash content in slurry B was determined according to the standard GB / T 508-85 Petroleum Products Ash Content Determination Method, and the deashing rate was calculated. The results are shown in Table 2.

[0111] Table 2

[0112]

[0113] As shown in Table 2, for a mixed catalytic system (containing both alkaline and acidic catalysts) of slurry oil, using deashing agent C alone resulted in a deashing rate of only 56.26%, with the ash content of the treated slurry exceeding 0.1%, which is insufficient for deep processing. However, the effect is still superior to commercially available slurry deashing agents. When deashing agent C and a commercially available deashing agent are added sequentially, the ash content of the treated slurry is between 0.04% and 0.06%, and the deashing rate can reach over 80%, regardless of the order of addition. Moreover, the addition of an amide-based slurry viscosity modifier further improves the deconsolidation effect, with a deashing rate exceeding 90%. When the deashing agent provided by this invention is mixed with a commercially available deashing agent, the deconsolidation effect disappears if the system becomes turbid.

[0114] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A deashing agent for slurry oil in an alkaline catalytic system, characterized in that, The deashing agent contains a charge neutralizer, a demulsifier, a dimer polyamide, and a solvent; The dimer acid polyamide is a condensation product of an aliphatic diacid and a polyamine. The aliphatic diacid is selected from at least one of C8-C44 linear diacids, dimer undecenoic acid, dimer olitic acid, dimer tetradecenoic acid, dimer palmitoleic acid, dimer oleic acid, dimer linoleic acid, dimer linolenic acid, dimer ricinoleic acid, dimer arachidonic acid, and dimer docosahexaenoic acid. The polyamine is selected from at least one of C2-C18 aliphatic diamines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, phenylenediamine, and cyclohexanediamine. The molecular weight of the dimer acid polyamide is 1000-10000. The charge neutralizing agent contains aliphatic amine polyoxyethylene ether. The demulsifier contains alkylphenol resin polyoxyethylene polyoxypropylene ether. The molecular weight of the alkylphenol resin is 3000-20000. The charge neutralizer comprises 2-10% by weight, the demulsifier comprises 2-15% by weight, the dimer acid polyamide comprises 10-40% by weight, and the balance is solvent.

2. The deashing agent according to claim 1, characterized in that, By weight percentage, the charge neutralizer is 5-8%, the demulsifier is 8-12%, and the dimer acid polyamide is 25-35%.

3. The deashing agent according to claim 1 or 2, characterized in that, The dimer acid polyamide is a condensation product of dimer oleic acid and octadecanediamine, a condensation product of dodecanoic acid and phenylenediamine, or a condensation product of dimer palmitic acid and triethylenetetramine.

4. The deashing agent according to claim 3, characterized in that, The molecular weight of the dimer acid polyamide is 3000-5000.

5. The deashing agent according to claim 1 or 2, characterized in that, In the fatty amine polyoxyethylene ether, the alkyl group in the fatty amine group is a C8-C24 alkyl group, and the number of repeating units in the polyoxyethylene ether is 2-30.

6. The deashing agent according to claim 5, characterized in that, In the fatty amine polyoxyethylene ether, the alkyl group in the fatty amine group is a C12-C18 alkyl group, and the number of repeating units in the polyoxyethylene ether is 10-18.

7. The deashing agent according to claim 1 or 2, characterized in that, The alkylphenol resin polyoxyethylene polyoxypropylene ether is a product of the contact reaction of alkylphenol resin, propylene oxide and ethylene oxide.

8. The deashing agent according to claim 7, characterized in that, The molecular weight of the alkylphenol resin is 8000-12000.

9. The deashing agent according to claim 8, characterized in that, In the alkylphenol resin, the alkyl group is a C4-C18 alkyl group.

10. The deashing agent according to claim 9, characterized in that, In the alkylphenol resin, the alkyl group is a C8-C12 alkyl group.

11. The deashing agent according to claim 10, characterized in that, The molar ratio of propylene oxide to ethylene oxide is 0.5-10:

1.

12. The deashing agent according to claim 11, characterized in that, The molar ratio of propylene oxide to ethylene oxide is 3-6:

1.

13. The deashing agent according to claim 1 or 2, characterized in that, The solvent contains aromatic solvent oil.

14. The deashing agent according to claim 13, characterized in that, The flash point of the aromatic solvent oil is higher than 60°C.

15. The deashing agent according to claim 14, characterized in that, The solvent also contains a co-solvent.

16. The deashing agent according to claim 15, characterized in that, The co-solvent is 5-20% by weight.

17. The deashing agent according to claim 16, characterized in that, The co-solvent content is 10-15%.

18. The deashing agent according to claim 17, characterized in that, The co-solvent is selected from at least one of ethylene glycol diethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, ethylene glycol ethyl acetate, propylene glycol methyl ether, propylene glycol ethyl ether, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether.

19. The use of the deashing agent according to any one of claims 1 to 18 in deashing oil slurry containing an alkaline catalyst.

20. The application according to claim 19, characterized in that, The oil slurry also contains an acidic catalyst.

21. A method for removing solid particles from oil slurry, characterized in that, The method includes the following steps: mixing the deashing agent according to any one of claims 1 to 18 with an oil slurry containing an alkaline catalyst and then subjecting it to sedimentation treatment.

22. The method according to claim 21, characterized in that, The conditions for the sedimentation treatment include at least the following: temperature of 80-130℃ and time of 12-72h.

23. The method according to claim 22, characterized in that, The weight ratio of the deashing agent to the alkaline catalyst is 0.05-0.1:1.

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