Process method for preparing clean aviation kerosene by converting low-carbon alcohol ether hydrocarbon

Abstract

The invention discloses a process method for preparing clean aviation kerosene by converting low-carbon alcohol ether hydrocarbon, which comprises the following steps of: performing alkylation / alkylation / reforming reaction on the low-carbon alcohol ether hydrocarbon to generate a mixed hydrocarbon product, and separating the mixed hydrocarbon product into a gas-phase component and a liquid-phase component; the liquid-phase component is further rectified to obtain light oil and heavy oil, the light oil is further converted into hydrocarbons with longer carbon chains through superposition, and the gas-phase component is converted into etherate through etherification reaction; separating the etherified product to obtain a gas-phase component and a liquid-phase component; the gas-phase component obtained through etherification is reused as a raw material, the heavy oil, the superimposed product and the etherified liquid-phase component are mixed to form clean aviation kerosene base oil, the clean aviation kerosene is obtained after needed additives are added, the raw materials are wide in source and renewable, the energy pressure is reduced, meanwhile, the raw material cost is reduced, and the process is simple, efficient and suitable for industrial production. The product is clean and environment-friendly, has economic and environmental benefits, and is suitable for industrial application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of energy chemical industry, in particular to a process method for preparing clean aviation kerosene by ether hydrocarbon conversion of low carbon alcohol. BACKGROUND

[0002] With the rapid development of global air transportation industry, the demand for aviation kerosene (SAF) continues to grow, and at the same time, in response to environmental pollution and energy crisis, it is urgent to seek sustainable alternative fuels. Bioaviation kerosene as a green and renewable energy source has broad application prospects.

[0003] Aviation kerosene is mainly composed of long-chain hydrocarbons, and the carbon chain length of these hydrocarbons is usually between C8 and C18, while the ideal carbon chain length is in the range of C8 to C16. Traditional aviation kerosene is mainly obtained by petroleum refining, however, the increasing depletion of petroleum resources and the increasing environmental protection requirements have prompted people to seek alternative raw materials and clean production processes.

[0004] At present, the preparation of aviation kerosene tends to be bioaviation kerosene preparation technology, and the existing bioaviation kerosene preparation technology mainly uses distillation method and high-pressure hydrocracking method. For the distillation method, the distillation process is easily affected by the raw material, and the product has high impurity content. If the oil product is stored for a long time, these impurities will cause the product color to further deepen due to chemical or physical action, thereby reducing the use performance of the oil product. The hydrocracking process has high severity to the raw material and high processing cost. SUMMARY

[0005] In order to overcome the above defects, the present application provides a process method for preparing clean aviation kerosene by ether hydrocarbon conversion of low carbon alcohol, which has wide raw material sources and is renewable, simple and efficient, clean and environmentally friendly, and has economic and environmental benefits, and is suitable for industrial application.

[0006] The technical scheme adopted by the present application to solve its technical problems is: a process method for preparing clean aviation kerosene by ether hydrocarbon conversion of low carbon alcohol, comprising the following steps:

[0007] Step one: sending low carbon alcohol ether hydrocarbon raw material into a fixed bed reactor, and performing at least one of hydrolysis, alkylation and reforming reaction in the presence of a catalyst to generate a mixed hydrocarbon product;

[0008] Step two: sending the mixed hydrocarbon product obtained in step one into a first separation tower, and separating the mixed hydrocarbon product at a temperature below 100℃ to obtain a gas phase component and a liquid phase component;

[0009] Step three: sending the gas phase component separated in step two into an etherification reactor to perform etherification reaction of mixed olefins and polyols to obtain an etherification product;

[0010] Step four: the liquid phase component separated in step two is sent into a rectification tower for rectification separation into light oil and heavy oil;

[0011] Step five: the light oil separated in step four is sent into a polymerization reactor for polymerization reaction through a catalyst to obtain a polymerization product;

[0012] Step six: the etherification product in step three is sent into a second separation tower for separation at a temperature below 100℃ to obtain a gas phase component and a liquid phase component;

[0013] Step seven: the gas phase component in step six is returned to the reactor in step one for reaction;

[0014] Step eight: the heavy oil in step four, the polymerization product in step five and the liquid phase component in step six are mixed into clean aviation kerosene base oil;

[0015] Step nine: one or more additives are added into the clean aviation kerosene base oil in step eight to obtain clean aviation kerosene.

[0016] Low-carbon alcohol ethers such as methanol and ethanol are used as raw materials, which are subjected to hydrocarbonization / alkylation / reforming reaction in the presence of a catalyst to generate mixed products containing C1-C16 hydrocarbons. The mixed products containing C1-C16 hydrocarbons are separated into a gas phase component and a liquid phase component through a first separation tower. The liquid phase component is further subjected to rectification to obtain light oil and heavy oil. The light oil is further converted into hydrocarbons with longer carbon chains through polymerization. The gas phase component is separated out for etherification. The gas phase component contains a large amount of light olefins, which can be converted into ether compounds through etherification reaction to improve the utilization rate of raw materials and the carbon chain length of products. Ultimately, etherification products with a carbon chain length of C6 or more are obtained. The etherification products are separated into a gas phase component and a liquid phase component. Ultimately, the heavy oil with a long carbon chain, the polymerization product and the etherification liquid phase component become clean aviation kerosene base oil. According to GB 6537 standard, various additives are added to obtain clean aviation kerosene.

[0017] As a further improvement of the present application, the reaction temperature in the fixed bed reactor in step one is 250-500, the pressure is 0.1-2 Mpa, and the space velocity is 0.1-1.

[0018] As a further improvement of the present application, the catalysts used in the step one, step three and step five are molecular sieve catalysts or solid acid catalysts containing silica, alumina and active ingredients, and the molecular sieve catalysts can be selected from ZSM-5 molecular sieve catalysts, SPAO-34 molecular sieve catalysts, Hβ molecular sieve catalysts, etc., wherein the catalysts in step one are mixed and packed in a certain proportion, and the hydrocarbation catalyst: alkylation catalyst: reforming catalyst = 0-0.6: 0-0.8: 0-0.8.

[0019] As a further improvement of the present application, the temperature of the first separation tower and the second separation tower is controlled below 100℃.

[0020] As a further improvement of the present application, the reaction temperature in the etherification reactor in step three is 50-200℃, and the reaction pressure is 0.1-3MPa.

[0021] As a further improvement of the present application, in step four, the overhead temperature of the rectifying tower is controlled at 150-180℃, the bottom temperature is controlled at 280-320℃, and the reflux ratio is 2-5.

[0022] As a further improvement of the present application, the reaction temperature in the polymerization reactor in step five is 80-500℃, the pressure is 1-5MPa, and the space velocity is 0.1-2.

[0023] As a further improvement of the present application, in step six, after the etherification reaction product is separated, the gas phase components are sent back to step one to continue to participate in the hydrocarbation, alkylation and reforming reactions. The olefins generally participate in the etherification reaction, and other low-carbon substances that do not react are returned to step one as raw materials to perform alkylation and reforming reactions, thereby improving the utilization rate.

[0024] As a further improvement of the present application, in step nine, the additive is a mixture of one or more of an anti-icing additive, an antistatic agent and an antioxidant, in addition, according to the GB 6537 standard, other additives such as anti-wear additives, metal deactivators, etc. can also be added, and the addition amount of various additives can be added according to the corresponding standard. The clean aviation kerosene base oil does not contain sulfur and metals such as aluminum, iron, lead, cobalt, etc. After adding the additive, it can meet the aviation kerosene standard, and can also be blended with traditional jet fuel for use or used as a traditional jet fuel quality improver.

[0025] The beneficial effects of the present application are: the present application uses low-carbon alcohol ether hydrocarbons such as methanol and ethanol as raw materials to prepare aviation kerosene, first, the low-carbon alcohol ether hydrocarbons are subjected to "hydrocarbonization / alkylation / reforming and other reactions" to generate mixed hydrocarbon products, and then the mixed hydrocarbon products are separated into gas phase and liquid phase components; the liquid phase components are further subjected to rectification to obtain light oil and heavy oil, the light oil is further converted into hydrocarbons with longer carbon chains through polymerization, and the gas phase components are converted into etherates through "etherification reaction"; the etherification products are separated to obtain gas phase components and liquid phase components; the heavy oil, the polymerization products and the etherification liquid phase components are mixed to become clean aviation kerosene base oil, and after adding anti-icing additives, antistatic agents, antioxidants and other additives, clean aviation kerosene is obtained. The raw materials of the present application are widely available and renewable, which reduces energy pressure, and at the same time, reduces the cost of raw materials. The process of the present application is simple and efficient, the product is clean and environmentally friendly, and has economic and environmental benefits, and is suitable for industrial application. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The system flowchart of the present application. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. Therefore, the detailed description of the embodiments of the present application provided below is not intended to limit the scope of the claimed present application, but only represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0028] Embodiment 1: A process for preparing clean aviation kerosene from low-carbon alcohol ether hydrocarbons, using methanol as a raw material, the specific steps are as follows:

[0029] Step one: hydrocarbonization / alkylation reaction: pump the methanol raw material into a fixed bed reactor, control the reaction temperature to be 350-500 DEG C, and the pressure to be 0.1-0.3 MPa in the presence of ZSM-5 molecular sieve catalyst (wherein the ratio of hydrocarbonization catalyst to alkylation catalyst is 1:2), and carry out hydrocarbonization and alkylation reaction to generate mixed hydrocarbon products;

[0030] Step two: first separation: send the mixed hydrocarbon products obtained in step one into a first separation column for separation under a temperature lower than 100 DEG C, the overhead of the first separation column obtains gas phase components, and the bottom of the first separation column obtains liquid phase components;

[0031] Step three: etherification reaction: the gas phase component obtained in step two is introduced into the etherification reactor, under the action of strong acid catalyst, the reaction temperature is controlled at 80-200℃, the pressure is controlled at 0.5-1.5 MPa, and the etherification reaction is carried out, to obtain the etherification product;

[0032] Step four: the liquid phase component separated in step two is sent into the rectifying column, the overhead temperature of the rectifying column is controlled at 150℃, the bottom temperature of the rectifying column is controlled at 300℃, and the reflux ratio is controlled at 3, to carry out the rectifying separation, to obtain the light oil and the heavy oil respectively.

[0033] Step five: the light oil separated in step four is sent into the polymerization reactor, under the condition of the presence of the molecular sieve catalyst, the reaction temperature is controlled at 230℃, the pressure is controlled at 3 MPa, to carry out the polymerization reaction;

[0034] Step six: the etherification product in step three is sent into the second separation column, to carry out the separation under the temperature condition of 100℃ or below, the overhead of the second separation column obtains the gas phase component, and the bottom of the second separation column obtains the liquid phase component;

[0035] Step seven: the gas phase component in step six is returned to the fixed bed reactor in step one to carry out the reaction;

[0036] Step eight: the heavy oil in step four, the polymerization product in step five, and the liquid phase component in step six are mixed to become the clean aviation kerosene base oil;

[0037] Step nine: a certain amount of anti-icing additive, anti-static agent, antioxidant, and other additives are added into the clean aviation kerosene base oil in step eight to make it meet the aviation kerosene standard.

[0038] Through the above process method, the clean aviation kerosene is successfully prepared, all indexes meet the relevant standards, the energy consumption in the production process is low, the raw material conversion rate can reach close to 100, the oil yield is >90%, and it has good industrial application prospect.

[0039] Example 2: a process method for preparing clean aviation kerosene by converting low-carbon alcohol ether hydrocarbon, the specific steps of which are as follows with ethanol as the raw material:

[0040] Step one: hydrocarbonization / alkylation reaction: the ethanol raw material is pumped into the fixed bed reactor, under the condition of the presence of the ZSM-5 molecular sieve catalyst, the reaction temperature is controlled at 350-500℃, the pressure is controlled at 0.1-0.3 MPa, to carry out the hydrocarbonization and alkylation reaction, to generate the mixed hydrocarbon product;

[0041] Step two: first separation: the mixed hydrocarbon product obtained in step one is sent to a first separation column for separation at a temperature below 100℃, the gas phase component is obtained at the top of the first separation column, and the liquid phase component is obtained at the bottom of the first separation column;

[0042] Step three: etherification reaction: the gas phase component obtained in step two is introduced into an etherification reactor, and the etherification reaction is carried out under the action of a strong acid catalyst, with the reaction temperature being controlled at 80-200℃ and the pressure being controlled at 0.5-1.5 MPa, to obtain an etherification product;

[0043] Step four: the liquid phase component separated in step two is sent to a rectification column, and the rectification separation is carried out with the top temperature of the rectification column being controlled at 150℃, the bottom temperature of the rectification column being controlled at 300℃, and the reflux ratio being controlled at 3, to obtain light oil and heavy oil respectively.

[0044] Step five: the light oil separated in step four is sent to a polymerization reactor, and the polymerization reaction is carried out in the presence of a molecular sieve catalyst, with the reaction temperature being controlled at 230℃ and the pressure being controlled at 3 MPa;

[0045] Step six: the etherification product in step three is sent to a second separation column for separation at a temperature below 100℃, the gas phase component is obtained at the top of the second separation column, and the liquid phase component is obtained at the bottom of the second separation column;

[0046] Step seven: the gas phase component in step six is returned to the fixed bed reactor in step one for reaction;

[0047] Step eight: the heavy oil in step four, the polymerization product in step five, and the liquid phase component in step six are mixed to obtain clean aviation kerosene base oil;

[0048] Step nine: a certain amount of anti-icing additives, anti-static agents, antioxidants and other additives are added to the clean aviation kerosene base oil in step eight to make it meet the aviation kerosene standard.

[0049] Through the above process, clean aviation kerosene is successfully prepared, all indexes meet the relevant standards, the energy consumption in the production process is low, the raw material conversion rate can reach nearly 100, the oil yield is > 90%, and it has good industrial application prospect.

[0050] Example 3: A process for preparing clean aviation kerosene from low-carbon alcohol ether hydrocarbon, the specific steps of which are as follows:

[0051] Step one: hydrocarbonization / alkylation reaction: low-carbon alcohol and low-carbon hydrocarbon are pumped into a fixed bed reactor, and the hydrocarbonization and alkylation reactions are carried out in the presence of a ZSM-5 molecular sieve catalyst, with the reaction temperature being controlled at 350-500℃ and the pressure being controlled at 0.1-0.3 MPa, to generate a mixed hydrocarbon product;

[0052] Step two: first separation: the mixed hydrocarbon product obtained in step one is sent to a first separation column, and separated at a temperature below 100℃, the gas phase component is obtained at the top of the first separation column, and the liquid phase component is obtained at the bottom of the first separation column;

[0053] Step three: etherification reaction: the gas phase component obtained in step two is introduced into an etherification reactor, and the etherification reaction is carried out under the action of a strong acid catalyst, with the reaction temperature being controlled at 80-200℃ and the pressure being controlled at 0.5-1.5 MPa, to obtain an etherification product;

[0054] Step four: the liquid phase component separated in step two is sent to a rectification column, and the rectification separation is carried out with the top temperature of the rectification column being controlled at 150℃, the bottom temperature of the rectification column being controlled at 300℃, and the reflux ratio being controlled at 3, to obtain light oil and heavy oil respectively.

[0055] Step five: the light oil separated in step four is sent to a polymerization reactor, and the polymerization reaction is carried out in the presence of a molecular sieve catalyst, with the reaction temperature being controlled at 230℃ and the pressure being controlled at 3 MPa;

[0056] Step six: the etherification product in step three is sent to a second separation column, and separated at a temperature below 100℃, the gas phase component is obtained at the top of the second separation column, and the liquid phase component is obtained at the bottom of the second separation column;

[0057] Step seven: the gas phase component in step six is returned to the fixed bed reactor in step one for reaction;

[0058] Step eight: the heavy oil in step four, the polymerization product in step five, and the liquid phase component in step six are mixed to become clean aviation kerosene base oil;

[0059] Step nine: a certain amount of anti-icing additives, anti-static agents, antioxidants and other additives are added to the clean aviation kerosene base oil in step eight to make it meet the aviation kerosene standard.

[0060] Through the above process, clean aviation kerosene is successfully prepared, all indexes of which meet the relevant standards, and the energy consumption in the production process is low, the raw material conversion rate can reach nearly 100, the oil yield is > 90%, and it has good industrial application prospect.

Claims

1. A process for the conversion of a lower alkanol ether to clean aviation kerosene, characterized by: The method comprises the following steps: Step 1: sending low-carbon alcohol ether hydrocarbon raw materials into a fixed bed reactor to perform at least one of hydrolysis, alkylation and reforming reactions in the presence of a catalyst to generate mixed hydrocarbon products; Step 2: sending the mixed hydrocarbon products obtained in Step 1 into a first separation tower to separate the mixed hydrocarbon products at a temperature below 100℃ to obtain gas phase components and liquid phase components; Step 3: sending the gas phase components separated in Step 2 into an etherification reactor to perform etherification reactions of mixed alkenes and polyols to obtain etherification products; Step 4: sending the liquid phase components separated in Step 2 into a rectification tower to perform rectification separation into light oil and heavy oil; Step 5: sending the light oil separated in Step 4 into a polymerization reactor to perform polymerization reactions through a catalyst to obtain polymerization products; Step 6: sending the etherification products in Step 3 into a second separation tower to perform separation at a temperature below 100℃ to obtain gas phase components and liquid phase components; Step 7: returning the gas phase components in Step 6 to the reactor in Step 1 to perform reactions; Step 8: mixing the heavy oil in Step 4, the polymerization products in Step 5 and the liquid phase components in Step 6 into clean aviation kerosene base oil; Step 9: adding one or more additives to the clean aviation kerosene base oil in Step 8 to obtain clean aviation kerosene.

2. The process for the conversion of a lower alkanol ether to clean aviation kerosene according to claim 1, characterized in that: The reaction temperature in the fixed bed reactor in Step 1 is 250-500, the pressure is 0.1-2 MPa, and the space velocity is 0.1-1.

3. The process for the conversion of a lower alkanol ether to clean aviation kerosene according to claim 1 or 2, characterized in that: The catalysts used in Steps 1, 3 and 5 are molecular sieve catalysts or solid acid catalysts containing silica, alumina and active ingredients.

4. The process for the conversion of lower alcohols to clean aviation kerosene of claim 1, wherein: The temperature of the first separation tower and the second separation tower is controlled below 100℃.

5. The process for the conversion of lower alcohols to clean aviation kerosene of claim 1, wherein: The reaction temperature in the etherification reactor in Step 3 is 50-200℃, and the reaction pressure is 0.1-3 MPa.

6. The process for the conversion of lower alcohols to clean aviation kerosene of claim 1, wherein: In Step 4, the overhead temperature of the rectification tower is controlled at 150-180℃, the bottom temperature is controlled at 280-320℃, and the reflux ratio is controlled at 2-5.

7. The process for the conversion of lower alcohols to clean aviation kerosene of claim 1, wherein: The reaction temperature in the polymerization reactor in Step 5 is 80-500℃, the pressure is 1-5 MPa, and the space velocity is 0.1-2.

8. The process for the conversion of lower alcohols to clean aviation kerosene of claim 1, wherein: After separation, the gas phase components in Step 6 are sent back to Step 1 to continue to participate in hydrolysis, alkylation and reforming reactions.

9. The process for the conversion of lower alcohols to clean aviation kerosene of claim 1, wherein: The additives in Step 9 are a mixture of one or more of anti-icing additives, antistatic agents and antioxidants.

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