CN112390699A - Method for reducing olefin - Google Patents
Method for reducing olefin Download PDFInfo
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- CN112390699A CN112390699A CN201910760581.1A CN201910760581A CN112390699A CN 112390699 A CN112390699 A CN 112390699A CN 201910760581 A CN201910760581 A CN 201910760581A CN 112390699 A CN112390699 A CN 112390699A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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Abstract
The invention relates to the field of olefin reduction, and discloses a method for reducing olefin, which comprises the following steps: contacting an aromatic hydrocarbon raw material with a catalyst to carry out alkylation reaction, wherein the alkylation reaction is carried out under the liquid phase condition of 100-300 ℃, the aromatic hydrocarbon raw material contains olefin and alkyl substituted aromatic hydrocarbon, and the content of propyl substituted aromatic hydrocarbon is not higher than 5 wt% based on the total amount of the alkyl substituted aromatic hydrocarbon. The method provided by the invention has requirements on the content of propyl-substituted aromatic hydrocarbon in the raw material, the method provided by the invention avoids the use of argil, and the activity and stability of the catalyst can be improved by adopting the method.
Description
Technical Field
The invention relates to the field of olefin reduction, in particular to a method for reducing olefin.
Background
Unsaturated hydrocarbons such as mono-olefins, multi-olefins and styrenic species, which are typically contained in aromatic hydrocarbon feedstocks, can lead to undesirable side reactions in downstream processes. Therefore, these unsaturated hydrocarbons should be removed by reaction before the aromatic feedstock is used in other processes.
The removal of unsaturated hydrocarbons from aromatic feedstocks is achieved commercially by employing hydrotreating processes. The method has high activity and stability, and can partially convert olefin therein into alkyl aromatic compound. However, the hydrotreating process usually employs a noble metal catalyst and is relatively expensive, and typical catalysts are disclosed in patent documents CN106268797B, CN1282733C, CN104342201B and CN 104014337B. In addition, for wide-component raw materials of aromatic hydrocarbons containing benzene, toluene and xylene at the same time, the hydrogenation reaction depth is difficult to be fully considered, and particularly, aromatic hydrocarbons with low boiling point such as toluene and the like are formed after the hydrogenation of the aromatic hydrocarbons with carbon nine or more, so that the loss of aromatic hydrocarbon products is large. The hydrogenation reaction has higher requirements on equipment, higher device cost, harsh reaction conditions and a certain loss rate of aromatic hydrocarbon. Therefore, there is a need in the industry for more efficient and economical processes.
Clay and molecular sieves have been reported to be useful in aromatic hydrocarbon feedstock processing. For clay, on the one hand, its service life is very short, usually only a few weeks; on the other hand, the exploitation of clay causes permanent environmental damage. In addition, the deactivated argil containing aromatic hydrocarbon is very harmful to human health, cannot be regenerated and recycled, and can only be treated by landfill, thus causing serious secondary pollution to the environment. With the increasing awareness of environmental protection, the problem is more and more concerned by the nation and the people, and the olefin removal technology capable of solving the problem is urgently needed by the production enterprises.
The molecular sieve has longer service life than the clay, is renewable, and can replace the clay under the condition of not changing the device. In view of the above advantages of molecular sieves, many research efforts and olefin removal catalysts prepared using molecular sieves as the main component have been disclosed. CN1618932A discloses a catalyst for catalytically refining and reforming aromatic oil under non-hydrogenation conditions, which is prepared by extruding kaolin, aluminum oxide and beta molecular sieve into strips, but the catalyst still has the defect of short service life, and the service life is less than one month. CN102220158A adopts a load type catalystA reagent containing at least one element or oxide selected from Ni, Mo, W or Zr, at least one element or oxide selected from Ti, Cu or Al and at least one rare earth element or oxide. In the initial period of operation, the disclosed catalyst has good performance, but the service life of the catalyst is still not ideal, and the weight space velocity is 0.3h-1The one-way service life of the catalyst can only reach four months under the condition of (2). CN107754846A reports a method for modifying molecular sieve by adding rear main group element, which interacts with lanthanide and alkali element to achieve better effect, but the preparation process of the method is relatively complicated and has more steps.
In addition, the olefin reducing molecular sieve catalyst which is industrially applied at present cannot be used alone generally, and still needs to be matched with clay for use. Therefore, there is a need to develop a method for reducing olefins without clay pretreatment and with better reactivity and stability.
Disclosure of Invention
The invention aims to solve the problems that the olefin reducing molecular sieve catalyst needs to be matched with clay for use and the stability of the catalyst needs to be further improved in the prior art, and provides the olefin reducing method.
The invention provides a method for reducing olefin, which comprises the following steps: contacting an aromatic hydrocarbon raw material with a catalyst to carry out alkylation reaction, wherein the alkylation reaction is carried out under the liquid phase condition of 100-300 ℃, the aromatic hydrocarbon raw material contains olefin and alkyl substituted aromatic hydrocarbon, and the content of propyl substituted aromatic hydrocarbon is not higher than 5 wt% based on the total amount of the alkyl substituted aromatic hydrocarbon.
Preferably, the propyl-substituted aromatic hydrocarbon content is not higher than 4% by weight, preferably 0-2% by weight, based on the total amount of said alkyl-substituted aromatic hydrocarbons.
Preferably, the ethyl-substituted aromatic hydrocarbon content is not higher than 20 wt.%, preferably not higher than 15 wt.%, more preferably 0 to 14 wt.%, based on the total amount of the alkyl-substituted aromatic hydrocarbons.
Preferably, the catalyst comprises a molecular sieve and optionally a binder, preferably the molecular sieve is a MWW molecular sieve; further preferably, the preparation method of the MWW molecular sieve comprises:
(1) mixing a silicon source, an aluminum source, an alkali source, a template agent and water, wherein the mixing is carried out at 0-15 ℃;
(2) carrying out hydrothermal treatment on the mixture obtained in the step (1) under a hydrothermal crystallization condition;
(3) roasting the solid product obtained in the step (2);
wherein the molar ratio of the silicon source, the aluminum source, the alkali source, the template agent and the water is 10: 0.2-2: 5-30: 0.5-10: 20-300, preferably 10: 0.5-1.5: 10-20: 0.5-5: 30-300, more preferably 10: 0.6-0.9: 14-18: 1-3: 40-200, wherein the silicon source is SiO2Calculated by Al as the aluminum source2O3Calculated as OH as alkali source-And (6) counting.
The inventor of the invention finds that the service life of the catalyst is closely related to the content of the propyl-substituted aromatic hydrocarbon in the alkyl-substituted aromatic hydrocarbon in the aromatic hydrocarbon raw material, the content of the propyl-substituted aromatic hydrocarbon in the alkyl-substituted aromatic hydrocarbon is too high, the blockage of molecular sieve pore channels, especially micropore pore channels, is easily caused, the content of the propyl-substituted aromatic hydrocarbon in the alkyl-substituted aromatic hydrocarbon is controlled, the stability of the catalyst can be improved, and the longer service life of the catalyst is ensured. In the process of further research, the inventor finds that controlling the content of methyl-substituted aromatic hydrocarbon in alkyl-substituted aromatic hydrocarbon in the aromatic hydrocarbon raw material to be not less than 75 wt% and the content of ethyl-substituted aromatic hydrocarbon to be not more than 20 wt% is more beneficial to further prolonging the service life of the catalyst. The inventor of the invention continuously researches and discovers that the MWW molecular sieve with larger acid weight can be prepared by mixing a silicon source, an aluminum source, an alkali source, a template agent and water at 0-15 ℃, and then carrying out hydrothermal treatment and roasting, when the molecular sieve is used for treating alkyl substituted aromatic hydrocarbon, when the content of propyl substituted aromatic hydrocarbon is not higher than 5 weight percent of raw material, the molecular sieve is more beneficial to removing olefin in the aromatic hydrocarbon raw material, and the catalyst has longer service life. The results of the examples show that the olefin conversion rate is still more than 70% and the aromatic hydrocarbon loss rate is below 0.5% after 10000h of reaction by adopting the method provided by the invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for reducing olefin, which comprises the following steps: contacting an aromatic hydrocarbon feedstock with a catalyst to perform an alkylation reaction, wherein the alkylation reaction is performed under liquid phase conditions of 100 ℃ and 300 ℃, wherein the aromatic hydrocarbon feedstock contains olefin and alkyl substituted aromatic hydrocarbon, and the content of propyl substituted aromatic hydrocarbon is not higher than 5 wt%, preferably not higher than 4 wt%, and more preferably 0-2 wt% based on the total amount of the alkyl substituted aromatic hydrocarbon.
The stability of the catalyst can be improved by controlling the content of the propyl-substituted aromatic hydrocarbon in the alkyl-substituted aromatic hydrocarbon, so that the longer service life of the catalyst is ensured.
According to the invention, the alkyl-substituted aromatic hydrocarbon is preferably an alkyl-substituted monocyclic aromatic hydrocarbon. Specifically, the alkyl-substituted aromatic hydrocarbon is a liquid alkyl-substituted aromatic hydrocarbon.
According to the present invention, preferably, the alkyl-substituted aromatic hydrocarbon comprises a methyl-substituted aromatic hydrocarbon, an optionally ethyl-substituted aromatic hydrocarbon and an optionally propyl-substituted aromatic hydrocarbon.
When the content of propyl-substituted aromatic hydrocarbons in the alkyl-substituted aromatic hydrocarbons in the aromatic hydrocarbon feedstock is greater than 5 wt.%, the method may further comprise adjusting the content of propyl-substituted aromatic hydrocarbons in the alkyl-substituted aromatic hydrocarbons to be not greater than 5 wt.%. The adjustment may be to remove part of the propyl-substituted aromatic hydrocarbon, or to introduce methyl-substituted aromatic hydrocarbon and/or ethyl-substituted aromatic hydrocarbon into the raw material to reduce the propyl-substituted aromatic hydrocarbon, which is not particularly limited in the present invention. Preferably, the adjusting method includes: methyl-substituted aromatic hydrocarbons are introduced into an aromatic hydrocarbon feedstock.
According to a preferred embodiment of the present invention, the content of methyl-substituted aromatic hydrocarbons is not less than 75% by weight, preferably 85-99.9% by weight, based on the total amount of alkyl-substituted aromatic hydrocarbons.
According to a preferred embodiment of the present invention, the content of ethyl-substituted aromatic hydrocarbons is not higher than 20 wt.%, preferably not higher than 15 wt.%, more preferably 0-14 wt.%, based on the total amount of alkyl-substituted aromatic hydrocarbons.
The inventor of the invention finds that controlling the content of propyl substituted aromatic hydrocarbon, methyl substituted aromatic hydrocarbon and ethyl substituted aromatic hydrocarbon in alkyl substituted aromatic hydrocarbon is more beneficial to further prolonging the service life of the catalyst.
According to the invention, the olefins comprise mono-olefins and/or di-olefins, preferably the mono-olefins content of the olefins is not less than 90% by weight, preferably 95-99.9% by weight. By adopting the preferred embodiment, the side reaction in the subsequent alkylation process is avoided, the yield and the quality of the alkylbenzene are further improved, and the service life of the catalyst is further prolonged. Specifically, the monoolefin may be an alkene, or may be an aromatic olefin.
According to a preferred embodiment of the present invention, the aromatic hydrocarbon feedstock has a gum content of not more than 200mg/100mL, preferably a gum content of not more than 120mg/100mL, more preferably not more than 60mg/100mL, for example 0-60mg/100 mL.
According to the present invention, the gum refers to solid matter in the feedstock, typically saturated monocyclic aromatic hydrocarbons and/or polycyclic aromatic hydrocarbons of C18 or greater, unless otherwise specified. In the reaction process, polycyclic aromatic hydrocarbon is not easy to generate ring-opening reaction and coking, which seriously affects the product quality, yield and the service life of the catalyst and is not beneficial to the alkylation reaction. The colloid content is measured by the method of GB/T8019-2008, when the boiling point of the raw material is close to that of the gasoline, the standard of the GB/T8019-2008 about the gasoline is adopted for measuring; when the boiling point of the raw material is close to that of the diesel oil, the standard of GB/T8019-2008 about the diesel oil is adopted for measurement.
The method provided by the invention preferably also comprises the step of pretreating the aromatic hydrocarbon raw material so that the colloid content in the raw material is not more than 200mg/100 mL. The method of pretreatment is not particularly limited in the present invention, as long as the colloid content in the aromatic hydrocarbon feedstock can be reduced to not more than 200mg/100 mL. For example, membrane filtration and distillation may be used to reduce the gums in the aromatic feedstock, and the specific procedures are known to those skilled in the art and are not described herein.
According to the present invention, preferably, the content of olefins in the aromatic hydrocarbon feedstock is between 0.1 and 10 wt.%, and the content of alkyl-substituted aromatic hydrocarbons is between 90 and 99.9 wt.%; preferably, the olefin content is from 0.1 to 5 wt%, and the alkyl-substituted aromatic hydrocarbon content is from 95 to 99.9 wt%; further preferably, the olefin content is from 0.1 to 3% by weight and the alkyl-substituted aromatic hydrocarbon content is from 97 to 99.9% by weight.
According to the present invention, the aromatic hydrocarbon feedstock may contain, in addition to gums, olefins, and alkyl-substituted aromatic hydrocarbons, saturated hydrocarbons, benzene, and the like.
According to the method for reducing olefins provided by the present invention, if the contents of the methyl-substituted aromatic hydrocarbon, the ethyl-substituted aromatic hydrocarbon and the propyl-substituted aromatic hydrocarbon in the alkyl-substituted aromatic hydrocarbon are not within the above ranges, the method may specifically further comprise adjusting the amounts of the methyl-substituted aromatic hydrocarbon, the ethyl-substituted aromatic hydrocarbon and the propyl-substituted aromatic hydrocarbon in the alkyl-substituted aromatic hydrocarbon so as to satisfy the above requirements. The specific adjustment method of the present invention is not particularly limited, and for example, when the content of the methyl-substituted aromatic hydrocarbon is small, the methyl-substituted aromatic hydrocarbon may be introduced into the raw material to increase the content of the methyl-substituted aromatic hydrocarbon.
In the present invention, the content of olefins, alkyl-substituted aromatics, methyl-substituted aromatics, ethyl-substituted aromatics and propyl-substituted aromatics in the aromatic hydrocarbon feedstock can be measured by a method of color quality analysis.
In the present invention, the methyl-substituted aromatic hydrocarbon refers to a methyl-based aromatic hydrocarbon in which a methyl group is connected to a benzene ring of an aromatic hydrocarbon, the ethyl-substituted aromatic hydrocarbon refers to an ethyl-based aromatic hydrocarbon in which an ethyl group is connected to a benzene ring of an aromatic hydrocarbon, and the propyl-substituted aromatic hydrocarbon refers to a propyl-based aromatic hydrocarbon in which a propyl group is connected to a benzene ring of an aromatic hydrocarbon. When at least two of methyl, ethyl and propyl groups are connected to the benzene ring of the aromatic hydrocarbon, the alkyl-substituted aromatic hydrocarbon is counted as an alkyl-substituted aromatic hydrocarbon with a high carbon atom number, that is, when the methyl and ethyl groups are simultaneously connected to the benzene ring of the aromatic hydrocarbon, the alkyl-substituted aromatic hydrocarbon is counted as an ethyl-substituted aromatic hydrocarbon, when the ethyl and propyl groups are simultaneously connected to the benzene ring of the aromatic hydrocarbon, the alkyl-substituted aromatic hydrocarbon is counted as a propyl-substituted aromatic hydrocarbon, and when the methyl, ethyl and propyl groups are simultaneously connected to the benzene ring of the aromatic hydrocarbon, the alkyl-substituted aromatic hydrocarbon is counted as a propyl-substituted aromatic hydrocarbon.
According to the present invention, 1 to 4 methyl groups may be attached to the benzene ring of the methyl-substituted aromatic hydrocarbon, and preferably, the methyl-substituted aromatic hydrocarbon is at least one selected from the group consisting of toluene, p-xylene, m-xylene, o-xylene, mesitylene, pseudocumene and durene.
According to the present invention, 1 or 2 ethyl groups may be attached to the benzene ring of the ethyl-substituted aromatic hydrocarbon, and preferably, the ethyl-substituted aromatic hydrocarbon is selected from at least one of ethylbenzene, o-diethylbenzene, m-diethylbenzene, and p-diethylbenzene.
According to the present invention, in the propyl-substituted aromatic hydrocarbon, the propyl group bonded to the benzene ring of the aromatic hydrocarbon may be an n-propyl group or an isopropyl group. Preferably, the phenyl ring of the propyl-substituted aromatic hydrocarbon has attached 1 or 2, preferably 1, propyl groups.
According to a preferred embodiment of the present invention, the propyl-substituted arene is n-propylbenzene and/or isopropylbenzene.
According to the invention, in particular, the catalyst may contain a molecular sieve and optionally a binder, preferably a molecular sieve and a binder.
The invention has wider selection range of the contents of the binder and the molecular sieve in the catalyst, and preferably, the content of the molecular sieve is 60-90 wt% and the content of the binder is 10-40 wt% based on the total amount of the catalyst; further preferably, the content of the molecular sieve is 70-80 wt%, and the content of the binder is 20-30 wt%.
According to the present invention, the binder may bind the molecular sieve particles together, and the binder may be an amorphous binder material. Preferably, the binder is selected from at least one of alumina, silica, kaolin, bentonite, montmorillonite and sepiolite, and is further preferably alumina.
The method for preparing the catalyst of the present invention is not particularly limited, and may be performed according to the conventional procedures in the art, for example, the method for preparing the catalyst may include:
a) extruding the molecular sieve and a binder and/or a precursor thereof into strips for molding to obtain a molding material;
b) and drying and roasting the formed product.
In the preparation process of the catalyst, a binder can be added, a precursor of the binder can be added, and the binder and the precursor of the binder can be added simultaneously. In the present invention, the binder precursor refers to a substance that can be converted into the binder by a subsequent firing step, and a person skilled in the art knows which binder precursor to select, knowing the kind of binder.
The present invention is not particularly limited in the manner of extruding in step a), and for example, the extruding may include: mixing the molecular sieve, the binder and/or a precursor thereof, water and an optional peptizing agent, and then extruding and molding the obtained mixture. The extrusion molding can be carried out in an extrusion molding machine.
According to the invention, preferably, a peptizing agent is added in the extrusion molding process. The peptizing agent may be at least one of inorganic acids, such as nitric acid.
The amount of the peptizing agent and water used in the present invention is selected from a wide range, for example, the amount of the peptizing agent may be 0.1 to 10 parts by weight and the amount of water may be 10 to 60 parts by weight, relative to 100 parts by weight of the molecular sieve and the binder and/or the precursor thereof.
The shape of the molded product is not particularly limited in the present invention, and may be appropriately selected according to actual needs, and may be, for example, a strip shape.
According to the catalyst provided by the invention, the drying and roasting in the step b) can be carried out according to the conventional technical means in the field, and the drying can be carried out at 50-180 ℃. The conditions for the firing may include: the temperature is 400-600 ℃, and the time is 2-100 h.
According to the invention, the preparation process of the catalyst can also comprise an ammonium exchange process, wherein the ammonium exchange process can be carried out before the extrusion molding in the step a), and specifically, the molecular sieve can be subjected to ammonium exchange to obtain a hydrogen type molecular sieve; the ammonium exchange process can also be carried out after the drying in the step b) and before the roasting, and specifically, the solid product obtained by the drying is subjected to ammonium exchange and then the roasting is carried out. The present invention is not particularly limited with respect to the specific operation and conditions of the ammonium exchange, and may be carried out according to the means conventional in the art, for example, the step of ammonium exchange may include: the molecular sieve or the solid product obtained by drying is contacted with ammonium nitrate solution. The ammonium exchange may be carried out a plurality of times, for example 2 to 5 times. The time for each ammonium exchange can be 0.5-5 h.
According to the present invention, preferably, the molecular sieve has a twelve-membered ring channel structure, and further preferably, the molecular sieve is at least one of a beta molecular sieve, a Y-type molecular sieve and an MWW molecular sieve. The preferred molecular sieves are more suitable for treating the aromatic hydrocarbon feedstock of the present invention and are more conducive to improving the stability and activity of the catalyst.
The invention has wider selection range of the Si/Al molar ratio of the molecular sieve, and preferably, SiO2/Al2O3In a molar ratio of 20 to 100: 1, more preferably 20 to 50: 1. in the present invention, the silica-alumina molar ratio of the molecular sieve can be determined by elemental analysis.
According to a more preferred embodiment of the invention, the molecular sieve is a MWW molecular sieve; preferably, the MWW molecular sieve has an acid amount of not less than 0.9mg NH3Per 100mg, more preferably not lessAt 1mg NH3Per 100mg, more preferably not less than 1.2mg NH3Per 100mg, more preferably 1.4-2.5mg NH3And/100 mg. The optimized molecular sieve is more favorable for further improving the catalytic activity and stability of the catalyst and further prolonging the service life of the catalyst.
Specifically, the acid content of the molecular sieve is measured by an ammonia adsorption method, and the acid content test method of the molecular sieve comprises the following steps: roasting the molecular sieve at 500 ℃ for 1h in air atmosphere, reducing the temperature to 25 ℃ and weighing, wherein the weight is recorded as a; then placing the calcined molecular sieve in a mixed gas of ammonia gas and nitrogen gas with the ammonia gas concentration of 5 vol% for 30min, then purging for 1h by using nitrogen gas, weighing, and recording the weight as b; the acid content of the molecular sieve is calculated according to the following formula (1):
the acid amount of the molecular sieve is (b-a)/a × 100% formula (1).
According to the present invention, in particular, the MWW molecular sieve has a monolayer lamellar structure. In the present invention, the monolayer lamellar structure means that the ratio of the smallest dimension (referred to as thickness) to the smallest dimension (referred to as length) of the three-dimensional dimensions of the molecular sieve is not more than 1/3. In the present invention, the structure of the MWW molecular sieve can be characterized by Scanning Electron Microscopy (SEM).
The MWW molecular sieve with the structure and the composition can further prolong the service life and the activity of the molecular sieve catalyst, and the preparation method of the MWW molecular sieve is not particularly limited. Preferably, the preparation method of the MWW molecular sieve comprises the following steps:
(1) mixing a silicon source, an aluminum source, an alkali source, a template agent and water, wherein the mixing is carried out at 0-15 ℃;
(2) carrying out hydrothermal treatment on the mixture obtained in the step (1) under a hydrothermal crystallization condition;
(3) roasting the solid product obtained in the step (2);
wherein the molar ratio of the silicon source, the aluminum source, the alkali source, the template agent and the water is 10: 0.2-2: 5-30: 0.5-10: 20-300, wherein the silicon source is SiO2Calculated by Al as the aluminum source2O3Calculated as OH as alkali source-And (6) counting.
According to a preferred embodiment of the invention, the mixing in step (1) is carried out at a temperature of 0 to 10 ℃, more preferably at a temperature of 2 to 10 ℃. The MWW molecular sieve prepared by the preferred embodiment has higher acid content, and the catalyst prepared by the obtained molecular sieve has higher catalytic activity and longer service life in the alkylation process.
In the mixing process of step (1), the order of adding the silicon source, the aluminum source, the alkali source, the template and the water is not particularly limited, as long as the mixing is carried out at 0-15 ℃. In the invention, the silicon source, the aluminum source, the alkali source, the template and the water can be directly mixed together, or at least two of the silicon source, the aluminum source, the alkali source, the template and the water can be mixed in advance, and then other residual materials are added.
According to the present invention, the adding amount of the aluminum source, the alkali source, the template and the water can be selected according to the amount of the silicon source, and preferably, the molar ratio of the silicon source, the aluminum source, the alkali source, the template and the water is 10: 0.5-1.5: 10-20: 0.5-5: 30-300 parts of; further preferably, the molar ratio of the silicon source, the aluminum source, the alkali source, the template agent and the water is 10: 0.6-0.9: 14-18: 1-3: 40-200.
According to the present invention, the silicon source may be an organic silicon source and/or an inorganic silicon source, preferably an inorganic silicon source. The organic silicon source may be silicate, and for example, may be selected from at least one of tetramethyl orthosilicate, tetraethyl orthosilicate, and tetrapropyl orthosilicate. Preferably, the inorganic silicon source is at least one of silica, silica sol and water glass, and more preferably, silica sol and/or water glass. The silica sol can be obtained commercially. The invention is used for SiO in silica sol2The content of (b) is not particularly limited, and may be, for example, 15 to 45% by weight.
According to the present invention, preferably, the aluminum source is an alkaline aluminum source, and further preferably, the aluminum source is at least one selected from the group consisting of metal aluminates, metal metaaluminates, aluminum hydroxide, aluminum powder, and aluminum oxide. The metal of the metal aluminate and the metal meta-aluminate are each independently preferably an alkali metal, and the alkali metal may be selected from at least one of Li, Na, K, and Rb, preferably Na.
According to the present invention, the alkali source is used for providing alkalinity to the synthesis raw material, and the selection range of the kind of the alkali source is wide, specifically, the alkali source is an inorganic alkali, preferably at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and calcium hydroxide, more preferably sodium hydroxide and/or potassium hydroxide, and still more preferably sodium hydroxide.
According to the present invention, preferably, the template is at least one selected from the group consisting of ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, piperidine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, and octadecylamine, and more preferably, hexamethyleneimine.
According to the present invention, the mixing time in step (1) is selected from a wide range, based on the uniform mixing of the silicon source, the aluminum source, the alkali source, the template and the water, and is preferably 0.1 to 10 hours, and more preferably 0.5 to 3 hours. According to a particular embodiment of the invention, the mixing of step (1) is carried out under stirring conditions. The stirring speed is not particularly limited in the present invention, and can be appropriately selected by those skilled in the art according to the actual situation.
According to the present invention, preferably, the hydrothermal crystallization conditions of step (2) include: the temperature is 100-200 ℃, and preferably is 120-190 ℃; the time is 5-200h, preferably 30-120 h. Specifically, the hydrothermal treatment may be performed under autogenous pressure conditions under closed conditions.
The mode of obtaining the solid product in the present invention is not particularly limited, and generally, the production method further includes: and (3) filtering and drying a product obtained by the hydrothermal treatment in the step (2) to obtain the solid product. The drying may be carried out at 50-180 ℃.
According to a preferred embodiment of the present invention, the firing conditions in step (3) include: the temperature is 400-600 ℃, and the time is 5-100 h.
The present invention provides a wide range of alkylation reaction conditions to allow alkylation of olefins with alkyl substituted aromatic hydrocarbons, preferably the alkylation reaction conditions are such that the olefin conversion is greater than 70%, preferably greater than 80%, and more preferably greater than 90%.
According to the method for reducing olefin provided by the invention, the alkylation reaction is preferably carried out at the temperature of 140-220 ℃, preferably 150-180 ℃, and more preferably 170-180 ℃.
Preferably, the alkylation reaction is carried out at a pressure of from 0.5 to 5MPa, preferably from 1 to 3MPa, the pressure being expressed as gauge pressure;
preferably, in the alkylation reaction, the mass space velocity of the aromatic hydrocarbon raw material is 0.1-50h-1Preferably 0.5 to 10h-1。
The olefin reduction method provided by the invention enables the catalyst to have high stability, and the duration of the alkylation reaction can be maintained to be more than 1 year under the optimal condition.
The present invention will be described in detail below by way of examples.
Example 1
The method for reducing olefin of the embodiment is carried out in a fixed bed reactor, the loading of the catalyst is 1g, and the catalysts A, B and C are respectively in contact reaction with the raw materials 1 and 2 under alkylation reaction conditions, wherein the alkylation reaction conditions comprise: the temperature is 177 ℃, the reaction pressure is 2MPa in gauge pressure, and the mass space velocity of the raw material is 2.5h-1。
The preparation method of the catalyst A comprises the following steps: a53 g sample of commercially available MCM-22 powder (commercially available from Nanjing Xiancheng nanomaterial science and technology Co., Ltd., trade name XFF09, SiO)2/Al2O327) was mixed with 17g of alumina, then 18g of 5% by weight nitric acid was added and kneaded, then strand-formed into a phi 1.6 × 2 mm strand on a strand-forming machine, dried at 120 ℃, exchanged with 5% by mass ammonium nitrate until 99.9% by weight of Na in the solid product was removed, and then calcined at 550 ℃ for 12 hours.
The preparation method of the catalyst B comprises the following steps: a54 g commercial Beta powder sample (commercially available from Nanjing Xiapong nanomaterial science and technology Co., Ltd., trade name XFF13, SiO)2/Al2O3In a molar ratio of 40) with 15g of alumina and then addingAdding 20g of 5 wt% nitric acid, kneading, extruding on a strip extruder to form strips with the diameter of 1.6 multiplied by 2 mm, drying at 120 ℃, exchanging with 5 wt% ammonium nitrate to remove 99.9 wt% Na in the solid product, and roasting at 550 ℃ for 12 hours.
The preparation method of the catalyst C comprises the following steps: a sample of 57g of a commercially available Y zeolite powder (commercially available from Nanjing Xiancheng nanomaterial science and technology Co., Ltd., trade name XFF10, SiO)2/Al2O3At a molar ratio of 5.3) with 17g of alumina, then 18g of 5% by weight nitric acid was added and kneaded, then the mixture was extruded into a rod-shaped form of phi 1.6 × 2 mm on an extruder, dried at 120 ℃, exchanged with 5% by mass ammonium nitrate until 99.9% by weight Na in the solid product was removed, and then calcined at 550 ℃ for 12 hours.
The compositions of feed 1 and feed 2 are listed in table 1.
The results of the 24h reaction are shown in Table 2 and the results of the 240h reaction are shown in Table 3.
Carrying out an alkylation stability test on the catalyst A, specifically, carrying out contact reaction on the catalyst A and the raw material 1 under alkylation conditions, wherein the alkylation conditions comprise: the temperature is 175 ℃, the gauge pressure is measured, the reaction pressure is 2MPa, and the mass space velocity of the raw material is 2h-1The results data for olefin conversion and aromatics loss for reactions 20h, 100h, 500h, 2000h, 5000h, and 10000h are shown in Table 4.
Comparative example 1
The procedure of example 1 was followed except that feed 1 was replaced with feed 3 by reacting catalysts A, B and C in contact with feed 3, respectively, the composition of feed 3 being as shown in Table 1. The results of the 24h reaction are shown in Table 2 and the results of the 240h reaction are shown in Table 3.
Example 2
Diluting a raw material 3 by using a mixed solution of xylene and ethylbenzene (the mass ratio of the xylene to the ethylbenzene is 3:1), filtering after dilution to reduce the colloid content to 75mg/100ml, wherein in a raw material 4 obtained after dilution, the content of methyl-substituted aromatic hydrocarbon is 86.5 wt%, the content of ethyl-substituted aromatic hydrocarbon is 10.9 wt%, and the content of propyl-substituted aromatic hydrocarbon is 2.6 wt% based on the total amount of alkyl-substituted aromatic hydrocarbon. The procedure of example 1 was followed, except that the starting material 1 was replaced with the starting material 4, namely, the catalysts A, B and C were respectively contact-reacted with the starting material 4. The results of the 24h reaction are shown in Table 2 and the results of the 240h reaction are shown in Table 3.
Example 3
The procedure of example 1 was followed except that feed 1 was replaced with feed 5 by reacting catalysts A, B and C in contact with feed 5, respectively, the composition of feed 5 being as shown in Table 1. The results of the 24h reaction are shown in Table 2 and the results of the 240h reaction are shown in Table 3.
Example 4
The procedure of example 1 was followed except that feed 1 was replaced with feed 6 by reacting catalysts A, B and C in contact with feed 6, respectively, the composition of feed 6 being as shown in Table 1. The results of the 24h reaction are shown in Table 2 and the results of the 240h reaction are shown in Table 3.
Example 5
The procedure of example 1 was followed, except that the catalysts D were used to contact and react with the starting materials 1 to 6, respectively. The preparation method of the catalyst D comprises the following steps:
(1) stirring and mixing silica sol, sodium aluminate, NaOH, hexamethyleneimine and water for 2 hours at the temperature of 8 ℃ to prepare a silicon source, an aluminum source, an alkali source, a template agent and water with the molar ratio of 10: 0.7: 17: 2.3: 120, wherein the silicon source is SiO2Calculated by Al as the aluminum source2O3Calculated as OH as alkali source-And (6) counting.
(2) The mixture is crystallized for 75h at 150 ℃, and then filtered and dried (120 ℃) to obtain a solid product.
(3) And (3) carrying out ammonium exchange on the solid product and an ammonium nitrate solution with the mass concentration of 5% until 99.9 wt% of Na in the solid product is removed.
(4) And roasting the product obtained by ammonium exchange at 500 ℃ for 20h to obtain the MWW molecular sieve. The molecular sieve has a monolayer lamellar structure and the acid content of the molecular sieve is 1.4mg NH according to the characterization by a Scanning Electron Microscope (SEM)3/100mg。
(5) Mixing the molecular sieve and the alumina binder according to the weight ratio of 7: 3 with a 2.5% nitric acid aqueous solution, wherein the amount of the nitric acid aqueous solution is 63 parts by weight relative to 100 parts by weight of the molecular sieve and the alumina. The resulting mixture was formed into a bar having a length of Φ 1.6 × 2 mm in a plodder. The resulting strands were dried at 100 ℃ for 6h and then calcined at 500 ℃ for 25h to give catalyst D. The results of the 24h reaction are shown in Table 2 and the results of the 240h reaction are shown in Table 3.
Example 6
The procedure of example 1 was followed except that the catalysts E were used to contact and react with the starting materials 1 to 6, respectively. The preparation of catalyst E was carried out in accordance with the preparation of catalyst D, except that in step (1), silica sol, sodium aluminate, NaOH, hexamethyleneimine and water were mixed at 27 ℃. The acid content of the prepared molecular sieve is 0.8mg NH3And/100 mg. The results of the 24h reaction are shown in Table 2 and the results of the 240h reaction are shown in Table 3.
TABLE 1
| Starting materials 1 | Raw material 2 | Raw material 3 | Starting Material 5 | Starting Material 6 | |
| Gum content, mg/100mL | 105 | 60 | 375 | 275 | 155 |
| Olefin content, wt.% | 1.4 | 0.8 | 2.6 | 1.7 | 1.5 |
| Content of monoolefin in the olefin,% by weight | 97.3 | 98.3 | 94.3 | 95.0 | 95.2 |
| Content of alkyl-substituted aromatic hydrocarbons,% by weight | 97.0 | 98.9 | 91.4 | 95.1 | 92.5 |
| Content of methyl-substituted aromatic hydrocarbons,% by weight | 80.2 | 85.8 | 78.4 | 82.9 | 74.5 |
| Content of ethyl-substituted aromatic hydrocarbons,% by weight | 16.5 | 13.1 | 15.8 | 14.2 | 21.5 |
| Content of propyl-substituted aromatic hydrocarbons,% by weight | 3.3 | 1.1 | 5.8 | 2.9 | 4.0 |
Note: in table 1, the olefin content and the alkyl-substituted aromatic hydrocarbon content are based on the aromatic hydrocarbon feedstock, and the methyl-substituted aromatic hydrocarbon, the ethyl-substituted aromatic hydrocarbon, and the propyl-substituted aromatic hydrocarbon content are based on the alkyl-substituted aromatic hydrocarbon.
In table 1, the raw materials 1 to 6 are aromatic hydrocarbon raw materials from Shanghai Gaoqian petrochemical industry, and the methyl-substituted aromatic hydrocarbons in the raw materials 1 to 6 are each independently selected from at least one of toluene, p-xylene, m-xylene, o-xylene, mesitylene, pseudocumene and durene; the ethyl-substituted aromatic hydrocarbons in the raw materials 1-6 are respectively and independently selected from at least one of ethylbenzene, o-diethylbenzene, m-diethylbenzene and p-diethylbenzene; the propyl-substituted aromatic hydrocarbons in feedstocks 1-6 are each independently n-propylbenzene and/or cumene.
TABLE 2 reaction 24h olefin conversion
| Name of catalyst | Starting materials 1 | Raw material 2 | Raw material 3 | Raw material 4 | Starting Material 5 | Starting Material 6 |
| A | 99.4％ | 99.7％ | 91.4％ | 99.4％ | 92.5％ | 92.0％ |
| B | 98.7％ | 99.2％ | 88.7％ | 98.8％ | 90.6％ | 89.6％ |
| C | 98.6％ | 98.9％ | 86.8％ | 98.7％ | 89.0％ | 88.1％ |
| D | 99.6％ | 99.9％ | 92.8％ | 99.6％ | 93.7％ | 94.1％ |
| E | 99.5％ | 99.7％ | 91.7％ | 99.5％ | 92.5％ | 92.6％ |
TABLE 3 reaction 240h olefin conversion
| Name of catalyst | Starting materials 1 | Raw material 2 | Raw material 3 | Raw material 4 | Starting Material 5 | Starting Material 6 |
| A | 95.3％ | 96.2％ | 66.0％ | 95.9％ | 70.4％ | 69.7％ |
| B | 92.6％ | 95.7％ | 50.2％ | 94.2％ | 66.0％ | 58.8％ |
| C | 91.9％ | 94.0％ | 53.5％ | 93.3％ | 69.7％ | 60.7％ |
| D | 95.8％ | 96.4％ | 71.4％ | 96.2％ | 76.8％ | 72.2％ |
| E | 95.6％ | 96.2％ | 68.1％ | 96.2％ | 75.4％ | 70.1％ |
TABLE 4 olefin conversion and aromatics loss for catalyst A with feed 1 at different reaction times
Wherein, the aromatic hydrocarbon loss rate calculation formula is as follows:
Saromatic hydrocarbons＝(M1 Aromatic hydrocarbons-M2 Aromatic hydrocarbons)/M1 Aromatic hydrocarbons×100％
Wherein S isAromatic hydrocarbonsIs the loss rate of aromatic hydrocarbons; m1 Aromatic hydrocarbonsThe mass of aromatic hydrocarbon in the raw material; m2 Aromatic hydrocarbonsIs the quality of aromatic hydrocarbon in the reaction product after the reaction.
As can be seen from the data in tables 2-4, the olefin reduction method provided by the invention has the advantages of high reaction stability and low aromatic hydrocarbon loss rate. After 10000h of reaction, the conversion rate of olefin is still more than 70 percent, and the loss rate of aromatic hydrocarbon is below 0.5 percent.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A method for reducing olefins, the method comprising: contacting an aromatic hydrocarbon raw material with a catalyst to carry out alkylation reaction, wherein the alkylation reaction is carried out under the liquid phase condition of 100-300 ℃, the aromatic hydrocarbon raw material contains olefin and alkyl substituted aromatic hydrocarbon, and the content of propyl substituted aromatic hydrocarbon is not higher than 5 wt% based on the total amount of the alkyl substituted aromatic hydrocarbon.
2. The process according to claim 1, wherein the content of propyl substituted aromatics is not higher than 4 wt.%, preferably 0-2 wt.%;
preferably, the propyl-substituted aromatic hydrocarbon is n-propylbenzene and/or isopropylbenzene.
3. The process according to claim 1 or 2, wherein the ethyl-substituted aromatic hydrocarbon content is not higher than 20 wt. -%, preferably not higher than 15 wt. -%, further preferably 0-14 wt. -%, based on the total amount of the alkyl-substituted aromatic hydrocarbons;
preferably, the ethyl-substituted aromatic hydrocarbon is selected from at least one of ethylbenzene, o-diethylbenzene, m-diethylbenzene, and p-diethylbenzene.
4. A process according to any one of claims 1 to 3, wherein the methyl-substituted aromatic hydrocarbon is present in an amount of not less than 75% by weight, preferably 85 to 99.9% by weight, based on the total amount of alkyl-substituted aromatic hydrocarbon;
preferably, the methyl-substituted aromatic hydrocarbon has 1 to 4 methyl groups attached to the benzene ring, and preferably, the methyl-substituted aromatic hydrocarbon is at least one selected from the group consisting of toluene, p-xylene, m-xylene, o-xylene, mesitylene, pseudocumene and durene.
5. The process according to any one of claims 1 to 4, wherein the aromatic hydrocarbon feedstock has a gum content of not more than 200mg/100mL, preferably not more than 120mg/100mL, more preferably not more than 60mg/100 mL.
6. The process of any one of claims 1-5, wherein the aromatic hydrocarbon feedstock has an olefin content of from 0.1 to 10 wt.%, and an alkyl-substituted aromatic hydrocarbon content of from 90 to 99.9 wt.%; preferably, the olefin content is from 0.1 to 5 wt% and the alkyl-substituted aromatic hydrocarbon content is from 95 to 99.9 wt%.
7. A process according to any one of claims 1 to 6, wherein the content of mono-olefins in the olefin is not less than 90% by weight, preferably 95 to 99.9% by weight.
8. The process of any of claims 1-7, wherein the catalyst comprises a molecular sieve and optionally a binder; the molecular sieve has a twelve-membered ring channel structure;
preferably, the molecular sieve is at least one of a beta molecular sieve, a Y-type molecular sieve and an MWW molecular sieve;
preferably, the binder is selected from at least one of alumina, silica, kaolin, bentonite, montmorillonite and sepiolite.
9. The process of claim 8, wherein the molecular sieve is a MWW molecular sieve;
preferably, the MWW molecular sieve has an acid amount of not less than 0.9mg NH3Per 100mg, more preferably not less than 1mg NH3Per 100mg, more preferably not less than 1.2mg NH3Per 100mg, more preferably 1.4-2.5mg NH3100 mg; the acid content of the MWW molecular sieve is measured by an ammonia adsorption method, and the acid content test method of the MWW molecular sieve comprises the following steps: roasting the molecular sieve at 500 ℃ for 1h in air atmosphere, reducing the temperature to 25 ℃ and weighing, wherein the weight is recorded as a; then placing the calcined molecular sieve in a mixed gas of ammonia gas and nitrogen gas with the ammonia gas concentration of 5 vol% for 30min, then purging for 1h by using nitrogen gas, weighing, and recording the weight as b; the acid content of the molecular sieve is calculated according to the following formula (1);
the acid amount of the molecular sieve is (b-a)/a × 100% formula (1);
preferably, the MWW molecular sieve has a monolayer sheet-like structure.
10. The process of claim 9, wherein the process for preparing the MWW molecular sieve comprises:
(1) mixing a silicon source, an aluminum source, an alkali source, a template agent and water, wherein the mixing is carried out at 0-15 ℃;
(2) carrying out hydrothermal treatment on the mixture obtained in the step (1) under a hydrothermal crystallization condition;
(3) roasting the solid product obtained in the step (2);
wherein the molar ratio of the silicon source, the aluminum source, the alkali source, the template agent and the water is 10: 0.2-2: 5-30: 0.5-10: 20-300, preferably 10: 0.5-1.5: 10-20: 0.5-5: 30-300, more preferably 10: 0.6-0.9: 14-18: 1-3: 40-200, wherein the silicon source is SiO2Calculated by Al as the aluminum source2O3Calculated as OH as alkali source-Counting;
preferably, the mixing of step (1) is carried out at 0-10 ℃, preferably at 2-10 ℃;
preferably, the mixing time in step (1) is 0.1 to 10 hours, and more preferably 0.5 to 3 hours.
11. The method of claim 10, wherein,
the silicon source is an inorganic silicon source, preferably at least one of silicon oxide, silica sol and water glass, and more preferably the silica sol and/or the water glass;
the aluminum source is at least one selected from metal aluminate, metal meta-aluminate, aluminum hydroxide, aluminum powder and aluminum oxide;
the alkali source is an inorganic alkali, preferably at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and calcium hydroxide, and more preferably sodium hydroxide and/or potassium hydroxide;
the template agent is at least one selected from ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, hexahydropyridine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine and octadecylamine.
12. The method of claim 10, wherein the hydrothermal crystallization conditions of step (2) comprise: the temperature is 100-200 ℃, and preferably is 120-190 ℃; the time is 5 to 200 hours, preferably 30 to 120 hours;
preferably, the roasting conditions in step (3) include: the temperature is 400-600 ℃, and the time is 5-100 h.
13. The process of any of claims 1-12, wherein the alkylation reaction conditions are such that olefin conversion is greater than 70%, preferably greater than 80%;
preferably, the alkylation reaction is carried out at 140-;
preferably, the alkylation reaction is carried out at a pressure of from 0.5 to 5MPa, preferably from 1 to 3MPa, the pressure being expressed as gauge pressure;
preferably, in the alkylation reaction, the mass space velocity of the aromatic hydrocarbon raw material is 0.1-50h-1Preferably 0.5 to 10h-1。
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