A method for recovering amine alcohol inactivating agents from ethylene oligomerization catalyst waste liquid

Abstract

This invention relates to the field of inactivator recovery technology, specifically a method for recovering amine / alcohol inactivators from ethylene oligomerization catalyst waste liquid. The method includes: injecting the ethylene oligomerization catalyst waste liquid and an inorganic salt treatment agent into a treatment vessel, where they are thoroughly mixed and reacted to obtain a premix; passing the premix through a solid filter to separate the filter residue and filtrate, thus completing the harmless conversion of the waste catalyst; injecting the filtrate into flash evaporator 1 for a first flash evaporation, and injecting the liquid phase from flash evaporator 1 into flash evaporator 2 for a second flash evaporation; cooling the gas phase separated by the second flash evaporation in a cooler to achieve the recovery of amine / alcohol inactivators. This invention first uses a low-cost inorganic salt treatment agent to convert the waste catalyst into a harmless solid, eliminating the need for traditional incineration and reducing environmental pollution; then, through two flash evaporation purification processes, amine / alcohol inactivators and hydrocarbon solvents can be recovered by distillation, reducing process costs.

Description

Technical Field

[0001] This invention relates to the field of inactivator recovery technology, specifically a method for recovering amine alcohol inactivators from ethylene oligomerization catalyst waste liquid. Background Technology

[0002] Currently, many existing ethylene oligomerization processes utilize long-chain amines / alcohols as catalyst deactivators. For example, patent CN1137509A describes a method for deactivating ethylene dimerization effluent using octyl / decylamine. Patent FR2581381 describes a method for treating a mixture of crude ethylene dimerization products using octyl / decylamine or dodecylamine. Patent CN109942362 describes a method for treating ethylene dimerization effluent using alcohols such as 2-ethylhexanol and 1-dodecanol. The use of catalyst deactivators prevents isomerization of α-olefins at distillation temperatures. Simultaneously, the relatively high boiling points of long-chain amines / alcohols effectively prevent them from entering the recovered ethylene and products through evaporation. After treatment, α-olefins in the reaction effluent are recovered, but it still contains derivatives formed by the amine / alcohol deactivator and catalyst / co-catalyst, high-boiling polymers, hydrocarbon solvents, etc. This waste liquid must be sent to a company with professional hazardous waste treatment qualifications for incineration.

[0003] However, this treatment method releases harmful substances, causing environmental pollution, and also results in the loss of high-value materials contained in the mixture. For example, the solid substances contained in the waste liquid will release harmful particulate matter such as aluminum oxide and titanium dioxide into the environment after incineration, affecting the atmospheric environment; the high-value long-chain amine / alcohol inactivators contained in the waste liquid will be lost during incineration, increasing the production cost of α-olefins, and long-chain amines (such as octylamine) are toxic, easily causing environmental damage, and thus increasing the cost of subsequent treatment. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a method for recovering amine / alcohol deactivators from ethylene oligomerization catalyst waste liquid. First, the waste catalyst is converted into a harmless solid using inorganic salts, reducing environmental pollution. Then, after two flash evaporation purification processes, amine / alcohol deactivators, hydrocarbon solvents, etc., can be recovered, reducing process costs.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a method for recovering amine alcohol inactivating agents from ethylene oligomerization catalyst waste liquid, comprising the following steps:

[0006] (1) Inject the waste liquid of ethylene oligomerization catalyst and inorganic salt treatment agent into the treatment vessel, and mix and react thoroughly in the vessel to obtain a premix;

[0007] (2) The premixed material is passed through a solid filter to separate the filter residue and filtrate, thus completing the harmless conversion of the waste catalyst;

[0008] (3) The filtrate is injected into flash evaporator 1 for the first flash evaporation. The liquid phase remaining in flash evaporator 1 consists of amine alcohol inactivating agents, high carbon olefins and polymers.

[0009] (4) The liquid phase in flash evaporator 1 is injected into flash evaporator 2 for a second flash evaporation. The main product of the separated gas phase is amine / alcohol inactivator.

[0010] (5) The gas phase separated by the second flash evaporation is cooled by a cooler to achieve the recovery of amine / alcohol inactivating agents.

[0011] Preferably, in step (1), the ethylene oligomerization catalyst waste liquid comprises, by mass percentage, 1.5-2.5% titanium-based catalyst Ti(OR1)4 and aluminum-based co-catalyst Al(R2). n X 3-n 1-2%, amine inactivator or alcohol inactivator 0.2-1%, ethylene oligomer 25-35%, inorganic salt treatment agent 60-70%.

[0012] Preferably, by mass percentage, the ethylene oligomer comprises 7-9% 1-butene, 2-4% 1-hexene, and 85-90% higher olefins and polymers.

[0013] Preferably, R1 and R2 are C1-C8 alkyl or aryl groups, selected from any one or a mixture of several of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, n-hexyl, 2-ethylhexyl, phenyl, 2-methylphenyl, 4-methylphenyl, and 2,6-dimethylphenyl; X is selected from bromine or chlorine atoms; and n is an integer from 1 to 3.

[0014] Preferably, the amine inactivator is any one or a mixture of several of cyclohexylamine, 2-ethylhexylamine, laurylamine, stearylamine, oleylamine, aniline, octylamine, decylamine, N-methylaniline, dibutylamine, and didecylamine; the alcohol inactivator is any one or a mixture of several of cyclohexanol, benzyl alcohol, 2-ethylhexanol, octanol, biphenyl alcohol, n-decanol, 2-butylhexanol, and lauryl alcohol.

[0015] Preferably, the inorganic salt treatment agent is a mixture of any of the following: calcium hydroxide, sodium hydroxide, potassium hydroxide, zinc hydroxide, sodium bicarbonate, hydrated sodium bicarbonate, calcium bicarbonate, potassium bicarbonate, aluminum bicarbonate, magnesium bicarbonate, ammonium bicarbonate, calcium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, lead carbonate, cobalt carbonate, magnesium carbonate, manganese carbonate, strontium carbonate, iron carbonate, barium carbonate, magnesium calcium carbonate, basic copper carbonate, sodium carbonate monohydrate, chalcopyrite, azurite, bismuthite, malachite, zeolite, montmorillonite, kaolinite, bentonite, zirconium oxide, and aluminum silicate.

[0016] Preferably, the inorganic salt treatment agent comprises, by weight percentage, 63.7% calcium bicarbonate, 33.1% montmorillonite, and 3.2% sodium hydroxide.

[0017] Preferably, the inorganic salt treatment agent comprises, by mass percentage, 47.6% sodium bicarbonate, 47.6% zeolite, and 4.8% sodium hydroxide.

[0018] Preferably, the inorganic salt treatment agent comprises, by weight percentage, 65.8% calcium bicarbonate, 29.6% kaolin, and 4.6% potassium hydroxide.

[0019] Preferably, in steps (3)-(4), the first flash temperature is 50-150℃ and the first flash pressure is 1-10atm; the second flash temperature is 250-400℃ and the second flash pressure is 1-10atm.

[0020] This invention provides a method for recovering amine alcohol inactivators from ethylene oligomerization catalyst waste liquid, which has the following advantages compared with the prior art:

[0021] This invention first uses inexpensive inorganic salt treatment agents to treat the waste catalyst in the waste liquid, converting impurities such as metals Al and Ti contained in the waste liquid into harmless solids. These solids can then be separated by filtration and disposed of in landfills, eliminating the need for traditional incineration and reducing environmental pollution. The filtered filtrate then undergoes two flash evaporation purification processes, allowing for the recovery of amine / alcohol inactivators and hydrocarbon solvents through distillation. This avoids the loss of high-value amine / alcohol inactivators (such as octylamine and octanol) and reduces process costs. Furthermore, the pre-treatment of solids and liquids prevents solids from interfering with the flash evaporation process. Attached Figure Description

[0022] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings:

[0023] Figure 1 This is a process diagram for recovering amine / alcohol inactivators from the waste liquid of the ethylene oligomerization catalyst of this invention. Detailed Implementation

[0024] The following embodiments are provided to illustrate the implementation of this application in detail, so that the process of how this application uses technical means to solve technical problems and achieve technical effects can be fully understood and implemented accordingly.

[0025] The data in the following examples are based on a process for the oligomerization of ethylene to 1-butene at a capacity of 50,000 tons / year. The streams used are 1-butene and 1-hexene as the main products, with C8+ (C 8+The waste catalyst is a byproduct containing both amine / alcohol deactivators and spent catalyst. Inorganic salt treatment agents are used to treat the titanium-based catalyst and aluminum-based co-catalyst, completely converting them into harmless landfillable solids such as titanium oxide and aluminum hydroxide. The amine / alcohol deactivators are recovered through flash evaporation. This process achieves harmless treatment of the spent catalyst and co-catalyst while reducing process costs and environmental pollution.

[0026] Example 1

[0027] A method for recovering amine deactivators from ethylene oligomerization catalyst waste liquid includes the following steps:

[0028] (1) Inject the waste liquid of ethylene oligomerization catalyst and inorganic salt treatment agent into the treatment vessel, and mix and react thoroughly in the vessel to obtain a premix;

[0029] (2) The premixed material is passed through a solid filter to separate the filter residue and filtrate, thus completing the harmless conversion of the waste catalyst;

[0030] (3) The filtrate is injected into flash evaporator 1 for the first flash evaporation. The liquid phase remaining in flash evaporator 1 consists of amine inactivators, high carbon olefins and polymers.

[0031] (4) The liquid phase in flash evaporator 1 is injected into flash evaporator 2 for a second flash evaporation. The main product of the separated gas phase is an amine inactivator.

[0032] (5) The gas phase separated by the second flash evaporation is cooled by a cooler to achieve the recovery of amine inactivators.

[0033] In this embodiment, the content of each raw material and product is shown in the table below.

[0034] Table 1 Content

[0035]

[0036]

[0037]

[0038] In this embodiment, the recovery rate of isooctylamine was 89.49%.

[0039] Example 2

[0040] A method for recovering amine deactivators from ethylene oligomerization catalyst waste liquid includes the following steps:

[0041] (1) Inject the waste liquid of ethylene oligomerization catalyst and inorganic salt treatment agent into the treatment vessel, and mix and react thoroughly in the vessel to obtain a premix;

[0042] (2) The premixed material is passed through a solid filter to separate the filter residue and filtrate, thus completing the harmless conversion of the waste catalyst;

[0043] (3) The filtrate is injected into flash evaporator 1 for the first flash evaporation. The liquid phase remaining in flash evaporator 1 consists of amine inactivators, high carbon olefins and polymers.

[0044] (4) The liquid phase in flash evaporator 1 is injected into flash evaporator 2 for a second flash evaporation. The main product of the separated gas phase is an amine inactivator.

[0045] (5) The gas phase separated by the second flash evaporation is cooled by a cooler to achieve the recovery of amine inactivators.

[0046] In this embodiment, the content of each raw material and product is shown in the table below.

[0047] Table 2 Content

[0048]

[0049]

[0050]

[0051]

[0052] In this embodiment, the recovery rate of isooctylamine was 89.31%.

[0053] Example 3

[0054] A method for recovering alcohol deactivators from ethylene oligomerization catalyst waste liquid includes the following steps:

[0055] (1) Inject the waste liquid of ethylene oligomerization catalyst and inorganic salt treatment agent into the treatment vessel, and mix and react thoroughly in the vessel to obtain a premix;

[0056] (2) The premixed material is passed through a solid filter to separate the filter residue and filtrate, thus completing the harmless conversion of the waste catalyst;

[0057] (3) The filtrate is injected into flash evaporator 1 for the first flash evaporation. The liquid phase remaining in flash evaporator 1 consists of alcohol inactivating agent, high carbon olefins and polymers.

[0058] (4) The liquid phase in flash evaporator 1 is injected into flash evaporator 2 for a second flash evaporation. The main product of the separated gas phase is an alcohol inactivator.

[0059] (5) The gas phase separated by the second flash evaporation is cooled by a cooler to recover the alcohol inactivator.

[0060] In this embodiment, the content of each raw material and product is shown in the table below.

[0061] Table 3 Content

[0062]

[0063]

[0064]

[0065] In this embodiment, the recovery rate of n-octanol was 90.89%.

[0066] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A process for recovering an amine / alcohol inactivator from an ethylene oligomerization catalyst effluent, characterized by, The method comprises the following steps: (1) injecting ethylene oligomerization catalyst waste liquid and inorganic salt treating agent into a treating kettle, and mixing and reacting in the kettle to obtain a premix; The inorganic salt treating agent comprises, in mass percentage, 63.7% of calcium bicarbonate, 33.1% of montmorillonite, and 3.2% of sodium hydroxide; or 47.6% of sodium bicarbonate, 47.6% of zeolite, and 4.8% of sodium hydroxide; or 65.8% of calcium bicarbonate, 29.6% of kaolin, and 4.6% of potassium hydroxide; (2) separating the filtrate and the residue by passing the premix through a solid filter, and completing the harmless conversion of the waste catalyst; (3) injecting the filtrate into a flash evaporator 1 to perform first flash evaporation, and the liquid phase remaining in the flash evaporator 1 is amine / alcohol inactivator and high-carbon olefin and polymer; The first flash evaporation temperature is 50-150 ℃, and the first flash evaporation pressure is 1-10 atm; (4) injecting the liquid phase in the flash evaporator 1 into a flash evaporator 2 to perform second flash evaporation, and the separated gas phase main product is amine / alcohol inactivator; The second flash evaporation temperature is 250-400 ℃, and the second flash evaporation pressure is 1-10 atm; (5) cooling the separated gas phase by a cooler to realize the recovery of the amine / alcohol inactivator.

2. The process for recovering amine / alcohol inactivator from an ethylene oligomerization catalyst spent liquor according to claim 1, characterized in that, The amine in the amine / alcohol inactivator is any one or mixture of several of cyclohexylamine, 2-ethyl-hexylamine, laurylamine, stearylamine, oleylamine, aniline, octylamine, decylamine, N-methylaniline, dibutylamine, and didecylamine; The alcohol in the amine / alcohol inactivator is any one or mixture of several of cyclohexanol, benzyl alcohol, 2-ethyl-hexanol, octanol, diphenylolpropane, n-decanol, 2-butylhexanol, and lauryl alcohol.

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