CN112390268B - MWW molecular sieve, preparation method and application thereof, catalyst and method for removing olefin from hydrocarbon oil - Google Patents
MWW molecular sieve, preparation method and application thereof, catalyst and method for removing olefin from hydrocarbon oil Download PDFInfo
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Abstract
The invention relates to the field of olefin removal from hydrocarbon oil, and discloses an MWW molecular sieve, a preparation method and application thereof, a catalyst and a method for olefin removal from hydrocarbon oil, wherein the acid content of the molecular sieve is not less than 0.9mg NH 3 Per 100mg. The preparation method of the molecular sieve comprises the following steps: 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, wherein the molar ratio of the silicon source to the aluminum source to the alkali source to the template agent to the water is 10:0.2-2:5-30:0.5-10:20-300, wherein the silicon source is SiO 2 Calculated by Al as the aluminum source 2 O 3 The alkali source is calculated as OH ‑ And (6) counting. The catalyst containing the MWW molecular sieve provided by the invention has a larger bulk ratio, is used for reducing the bromine index of an aromatic hydrocarbon raw material by at least 60% in the process of reducing olefin, and has good stability.
Description
Technical Field
The invention relates to the field of olefin removal of hydrocarbon oil, in particular to an MWW molecular sieve, a preparation method and application thereof, a catalyst and a method for olefin removal of hydrocarbon oil.
Background
The aromatic hydrocarbon raw material mainly comes from processes such as petroleum reforming and cracking, generally comprises benzene, toluene, xylene, trimethylbenzene and the like, and can be used as a raw material of various petrochemical processes. However, since the aromatic hydrocarbon feedstock often contains unsaturated hydrocarbons, such as mono-olefins, multi-olefins, and styrene, which may affect downstream side reactions and product quality, and is not suitable for the application of the aromatic hydrocarbon feedstock, the aromatic hydrocarbon feedstock needs to be treated in advance to reduce the content of unsaturated hydrocarbons.
Olefins (mono-and poly-olefins) in aromatic feedstocks are removed industrially by hydrotreating processes. Commercial hydroprocessing catalysts have proven to be active, stable, to convert substantially the multiolefins contained in the aromatic hydrocarbon feedstock to oligomers and to partially convert the olefins to alkylaromatics. However, such catalysts require noble metal loading and have high operational requirements for the plant.
The method for removing unsaturated hydrocarbons by treating aromatic hydrocarbon raw materials with clay is widely applied to the fields of petroleum and chemical industry, but the clay has short treatment and use period, generally needs to be replaced within weeks, cannot be regenerated, has large solid waste amount and is not beneficial to environmental protection.
Molecular sieves can also be used as catalysts for reducing unsaturated hydrocarbons in feedstocks, and have the advantages of long service life and low solid waste compared to clays. WO0130942A1 discloses olefin eliminating catalyst prepared with mesoporous molecular sieve MCM-22 as active component and clay carrier, and has olefin eliminating rate higher than 95%. CN1618932A discloses a method for catalytically refining aromatic oil under non-hydrogenation conditions, which is characterized in that the aromatic oil passes through a catalyst bed layer and undergoes a dealkenation reaction under the non-hydrogenation conditions, wherein the reaction conditions are as follows: the reaction temperature is 100-300 ℃, the reaction pressure is 0.5-2.0MPa, and the space velocity is 0.5-40h -1 . The method disclosed by the method can remove trace olefin in aromatic hydrocarbon, but although the catalyst can be regenerated and reused, the single-pass life of the catalyst is still short, and the space velocity is 15h -1 Under the condition, the activity is reduced to 50% after 18 hours of evaluation, so that the industrial application is greatly limited.
Molecular sieves are generally more expensive than clays, and therefore, the useful life and good activity of molecular sieve catalysts are a prerequisite for commercial applications. Although the activity or service life of the molecular sieve is improved to a certain extent in the prior art, on one hand, the improvement degree is limited, and on the other hand, the molecular sieve with longer service life and good activity is difficult to obtain. Therefore, there is a need to develop a molecular sieve having both a long service life and good activity.
Disclosure of Invention
The invention aims to solve the problem that a molecular sieve cannot have both long service life and good activity in the olefin removal process of hydrocarbon oil in the prior art, and provides an MWW molecular sieve, a preparation method and application thereof, a catalyst and a method for olefin removal of hydrocarbon oil. The molecular sieve provided by the invention has longer service life and better activity when being used in the olefin removal process of hydrocarbon oil.
In order to achieve the above object, the present invention provides in a first aspect an MWW molecular sieve having an acid amount of not less than 0.9mg NH 3 /100mg。
Preferably, the molecular sieve has an acid content of not less than 1mg NH 3 Per 100mg, preferably not less than 1.2mg NH 3 Per 100mg, more preferably 1.2-2.5mg NH 3 /100mg。
In a second aspect, the present invention provides a method for preparing an MWW molecular sieve, wherein the method 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, wherein the silicon source is SiO 2 In terms of aluminum source, al is calculated 2 O 3 The alkali source is calculated as OH - And (6) counting.
Preferably, the mixing of step (1) is carried out at 0-10 ℃, preferably at 2-10 ℃.
Preferably, the molar ratio of the silicon source, the aluminum source, the alkali source, the template agent and the water is 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.
In a third aspect of the present invention, there is provided an MWW molecular sieve obtained by the process of the second aspect.
In a fourth aspect, the present invention provides the use of the MWW molecular sieve described in the first and third aspects above in the olefin removal of hydrocarbon oils.
In a fifth aspect, the present invention provides a catalyst comprising an MWW molecular sieve and a binder, wherein the MWW molecular sieve is the MWW molecular sieve of the first and third aspects.
In a sixth aspect, the present invention provides a process for the deolefination of a hydrocarbon oil, the process comprising: contacting the hydrocarbon oil with a catalyst under olefin removal conditions, wherein the catalyst is the catalyst of the fifth aspect.
The inventor of the invention finds in the research process that a silicon source, an aluminum source, an alkali source, a template and water are mixed at 0-15 ℃, and then hydrothermal treatment and roasting are carried out, so that the catalyst with a large acid content (not less than 0.9mg NH) can be prepared 3 Per 100mg, preferably not less than 1mg NH 3 Per 100mg, more preferably not less than 1.2mg NH 3 Per 100mg, more preferably 1.2-2.5mg NH 3 Per 100 mg) of MWW molecular sieve. Preferably, the molecular sieve has a monolayer lamellar structure, the packing is more compact, and the catalyst containing the MWW molecular sieve provided by the invention has a larger bulk ratio (preferably not less than 0.38g/ml, more preferably not less than 0.4g/ml, and more preferably 0.4-0.65 g/ml).
When the catalyst provided by the invention is applied to the process of reducing olefin from an aromatic hydrocarbon raw material, the bromine index of the raw material is reduced by at least 60%. From the comparison of the data of example 1 and example 7 of the present invention, it can be seen that the catalyst provided by the present invention has good stability. In addition, the catalyst provided by the invention does not need to load noble metal, so that the production cost is greatly reduced.
Drawings
FIG. 1 is an SEM image of a molecular sieve prepared in example 1 of the present invention;
figure 2 is an XRD pattern of the molecular sieve prepared in example 1 of the present 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.
In a first aspect, the present invention provides an MWW molecular sieve having an acid content of not less than 0.9mg NH 3 Per 100mg. The molecular sieve provided by the invention has higher acid content, so that the molecular sieve has higher catalytic activity and longer service life.
Preferably, the molecular sieve has an acid content of not less than 1mg NH 3 Per 100mg, preferably not less than 1.2mg NH 3 Per 100mg, more preferably 1.2-2.5mg NH 3 Per 100mg. The adoption of the preferred embodiment is more beneficial to further improving the catalytic activity of the molecular sieve and further prolonging the service life of the molecular sieve.
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 = (b-a)/a × 100% formula (1).
The weighing can be carried out using an apparatus of type XPE105DR, commercially available from Mettler corporation.
The acid content of MWW molecular sieves disclosed in the prior art is generally less than 0.9mg NH 3 /100mg。
According to the present invention, specifically, as shown in fig. 1, the 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 molecular sieve can be characterized by Scanning Electron Microscopy (SEM).
The MWW molecular sieve has a wide selection range of element compositions, and preferably, the molecular sieve has a silicon-aluminum molar ratio of 20-100:1, more preferably 20 to 50:1. the silica to alumina molar ratio of the molecular sieve can be determined by elemental analysis.
In a second aspect, the present invention provides a method for preparing an MWW molecular sieve, wherein the method 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, wherein the silicon source is SiO 2 Calculated by Al as the aluminum source 2 O 3 Calculated 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 ℃, preferably at a temperature of 2 to 10 ℃. The molecular sieve prepared by the preferred embodiment has higher acid content, and the catalyst prepared by the obtained molecular sieve has higher activity and longer service life in the olefin removal 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 preparation method provided by the 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.
Preferably, the molar ratio of the silicon source to the alkali source is 10:10-20, more preferably 10:14-18, wherein the silicon source is SiO 2 Calculated as OH as alkali source - And (6) counting. In the research process, the inventor of the present invention finds that, when the mixing of step (1) is performed at 0-15 ℃ and the molar ratio of the silicon source to the alkali source is controlled within the above range, the molecular sieve with better olefin removal performance can be prepared, and the catalyst prepared by the molecular sieve has higher olefin removal activity and longer service life when being used in the olefin removal process.
According to the preparation method provided by the invention, specifically, the silicon source is an organic silicon source and/or an inorganic silicon source, and preferably an inorganic silicon source. The organic silicon source may be a silicate including, but not limited to, tetramethyl orthosilicate, tetraethyl orthosilicate, 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 sol 2 The content of (b) is not particularly limited, and may be, for example, 15 to 45% by weight.
According to the preparation method provided by the invention, preferably, the aluminum source is an alkaline aluminum source, and further preferably, the aluminum source is at least one selected from metal aluminates, metal meta-aluminates, aluminum hydroxide, aluminum powder and aluminum oxide. The metal in the metal aluminate and the metal meta-aluminate are each independently preferably an alkali metal, and the alkali metal may be at least one selected from Li, na, K, and Rb, and preferably Na. The present invention is exemplified by sodium aluminate as the aluminum source, and the present invention is not limited thereto.
According to the preparation method provided by the invention, the alkali source is used for providing alkalinity for synthesis raw materials, preferably, the alkali source is an inorganic alkali, further 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 further preferably sodium hydroxide.
According to the present invention, preferably, the template is selected from at least one of ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, hexahydropyridine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, and octadecylamine. The hexamethylene imine is taken as an example for illustrative purposes in the examples of the present invention, and the present invention is not limited thereto.
According to the preparation method provided by the invention, the mixing time in the step (1) is selected within a wide range, based on uniformly mixing the silicon source, the aluminum source, the alkali source, the template and the water, preferably, the mixing time is 0.1-10h, and more preferably 0.5-3h. 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 preparation method provided by the present invention, preferably, the hydrothermal crystallization conditions in step (2) include: the temperature is 100-200 ℃, preferably 120-190 ℃; the time is 5-200h, preferably 30-120h.
Specifically, the hydrothermal treatment may be performed under a closed condition under autogenous pressure conditions.
The present invention is not particularly limited in the manner of obtaining the solid product, and in general, the production method further comprises: and (3) filtering and drying the 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 the preparation method provided by the invention, preferably, the preparation method further comprises the following steps: and (3) before roasting in the step (3), performing ammonium exchange on the solid product obtained in the step (2). The hydrogen form of the molecular sieve can be prepared by the ammonium exchange, and the invention has no particular limitation on the specific operation and conditions of the ammonium exchange, and can be carried out according to the conventional technical means in the field, for example, the step of ammonium exchange can comprise: contacting the solid product with a solution of ammonium nitrate. 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 0.5-5h.
According to a preferred embodiment of the present invention, the firing conditions in step (3) include: the temperature is 400-600 ℃, preferably 450-550 ℃; the time is 10-100h, preferably 24-35h.
In a third aspect, the present invention provides the MWW molecular sieve prepared by the preparation method described in the second aspect of the present invention. The acid amount, structure and composition of the MWW molecular sieve are the same as those of the MWW molecular sieve provided by the first aspect of the invention, and the description of the invention is omitted.
In a fourth aspect the invention provides the use of the MWW molecular sieve of the first and third aspects in the olefin removal of hydrocarbon oils. The MWW molecular sieve provided by the invention has higher activity and longer service life when being used in the olefin removal reaction process of hydrocarbon oil.
In a fifth aspect, the present invention provides a catalyst comprising an MWW molecular sieve and a binder, the MWW molecular sieve being the MWW molecular sieve of the above first and third aspects of 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.
According to a preferred embodiment of the present invention, the MWW molecular sieve is present in an amount of from 55 to 90 wt.%, more preferably from 60 to 80 wt.%, based on the total amount of catalyst; the content of the binder is 10 to 45 wt%, and further 20 to 40 wt%.
The catalyst containing the MWW molecular sieve provided by the invention has larger bulk ratio, and preferably, the bulk ratio of the catalyst is not less than 0.38g/ml, preferably not less than 0.4g/ml, and more preferably 0.4-0.65g/ml.
The present invention is not particularly limited to the method for producing the catalyst, as long as the catalyst having the above composition can be obtained, and preferably, the method for producing the catalyst comprises:
a) Extruding the MWW molecular sieve and a binder and/or a precursor thereof into strips for molding to obtain a molding;
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 also be added, and the binder and the precursor of the binder can also 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 to the manner of the extrusion molding in step a), and the extrusion molding includes, for example: mixing MWW molecular sieve, binder and/or precursor thereof, water and optional peptizing agent, and then extruding the obtained mixture to form strips. 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, and 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 MWW 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 5-100h.
In a sixth aspect, the present invention provides a process for the deolefination of a hydrocarbon oil, the process comprising: contacting the hydrocarbon oil with a catalyst under olefin removal conditions, wherein the catalyst is the catalyst of the fifth aspect.
The catalyst provided by the invention is suitable for removing olefin from various hydrocarbon oil raw materials. Preferably, the hydrocarbon oil comprises an aromatic stream obtained from a reforming or cracking process. The aromatic stream may include a variety of hydrocarbons, such as paraffins, aromatics, and bromine-reactive compounds (e.g., olefins). Generally, the aromatic stream comprises monocyclic aromatic hydrocarbons and undesirable olefins (including mono-olefins, poly-olefins, and styrene).
The unsaturated hydrocarbon content of hydrocarbon oils can be quantified using the Bromine Index (BI), which represents the number of milligrams of bromine consumed by 100 grams of sample. The higher the bromine index, the higher the unsaturated hydrocarbon content in the sample. Preferably, the hydrocarbon oil has a BI of 200 to 5000mg Br per 100g oil.
In the method provided by the invention, the hydrocarbon oil may contain nitrogen-containing impurities and/or sulfur-containing impurities, and the nitrogen-containing impurities and/or the sulfur-containing impurities may reduce the recycling time of the catalyst. The above impurities are preferably at least partially removed from the hydrocarbon oil prior to contacting the hydrocarbon oil with the catalyst used in the process provided by the present invention. The method for removing the impurities in the present invention is not particularly limited, and those skilled in the art can carry out the method according to the conventional techniques.
According to the method provided by the invention, the contact preferably enables unsaturated hydrocarbons in hydrocarbon oil to be converted into alkyl aromatic hydrocarbons.
Preferably, the de-olefination conditions include: the temperature is 100-250 ℃, the gauge pressure is 1-5MPa, and the mass space velocity is 0.5-50h -1 。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the acid amount of the molecular sieve was measured by an ammonia adsorption method, and the method for measuring the acid amount of the molecular sieve specifically included: 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);
acid amount of molecular sieve = (b-a)/a × 100% formula (1);
wherein the weighing was performed using a model XPE105DR instrument commercially available from Mettler corporation.
The morphological analysis of the molecular sieves was carried out by Scanning Electron Microscopy (SEM) commercially available from Philip under the model XL-30.
The silica to alumina molar ratio of the molecular sieve was determined using an elemental analyzer.
Example 1
(1) Mixing silica Sol (SiO) 2 The content is 40 wt%, the same below), sodium aluminate, naOH, hexamethyleneimine and water are stirred and mixed for 2 hours at the temperature of 4 ℃, and the molar ratio of the prepared silicon source, aluminum source, alkali source, template agent and water is 10:0.7:16:2:100, wherein the silicon source is SiO 2 In terms of aluminum source, al is calculated 2 O 3 Calculated as OH as alkali source - And (6) counting.
(2) The mixture is crystallized for 70h 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 30h to obtain the molecular sieve A-1.
The SEM picture of the molecular sieve A-1 is shown in FIG. 1, and it can be seen from FIG. 1 that the molecular sieve has a monolayer lamellar structure. The XRD pattern of the molecular sieve A-1 is shown in figure 2, and the molecular sieve A-1 is an MWW molecular sieve by comparing with the standard pattern.
The acid content of molecular sieve A-1 was found to be 1.5mg NH by analysis 3 100mg, and the molar ratio of silicon to aluminum is 28.
(5) Taking the molecular sieve A-1 and an alumina binder according to the weight ratio of 7:3, and a nitric acid aqueous solution having a mass concentration of 2.5%, wherein the nitric acid aqueous solution is used in an amount of 60 parts by weight based on 100 parts by weight of the molecular sieve a-1 and the alumina. The resulting mixture was formed into a strand having a diameter of 1.5mm in a plodder. The obtained strip-shaped molded product was dried at 100 ℃ for 6 hours and then calcined at 500 ℃ for 50 hours to obtain catalyst C-1. The bulk ratio of catalyst C-1 was 0.42g/ml.
(6) A process for the deolefination of a hydrocarbon oil, in particular:
will be described inThe catalyst C-1 is respectively contacted with three hydrocarbon oils containing olefin (the specific composition and properties are listed in the following table 1) to carry out the olefin removal reaction, and the reaction conditions comprise that: the temperature is 170 ℃, the gauge pressure is 2.0MPa, and the mass space velocity is 4h -1 The results of the reaction for 6 hours are shown in Table 2.
Comparative example 1
A molecular sieve, a catalyst, and a hydrocarbon oil dealkenation reaction were prepared according to the method of example 1, except that, in the step (1), silica sol, sodium aluminate, naOH, hexamethyleneimine, and water were mixed with stirring at 25 ℃ for 2 hours. The acid content of the prepared molecular sieve DA-1 is 0.8mg NH 3 Per 100mg. The bulk ratio of catalyst DC-1 was 0.37mg/ml. The results of the hydrocarbon oil deolefination reaction are shown in Table 2.
Example 2
(1) Stirring and mixing silica sol, sodium aluminate, naOH, hexamethyleneimine and water for 3 hours at the temperature of 2 ℃ to prepare a silicon source, an aluminum source, an alkali source, a template agent and water with the molar ratio of 10:0.8:18:2:150, wherein the silicon source is SiO 2 Calculated by Al as the aluminum source 2 O 3 Calculated as OH as alkali source - And (6) counting.
(2) The mixture is crystallized for 80h at 150 ℃, and then filtered and dried (120 ℃) to obtain a solid product.
(3) Ammonium exchange was carried out in the same manner as in step (3) of example 1.
(4) And roasting the product obtained by ammonium exchange at 480 ℃ for 24 hours to obtain the molecular sieve A-2.
The XRD pattern and SEM image of the molecular sieve A-2 are respectively similar to those of the molecular sieve A-1, and the molecular sieve A-2 is proved to be MWW molecular sieve and to have a single-layer sheet-like structure.
The acid content of molecular sieve A-2 was found to be 1.8mg NH by analysis 3 100mg, and the molar ratio of silicon to aluminum is 25.
(5) A catalyst was prepared in the same manner as in step (5) in example 1, except that molecular sieve A-1 was replaced with molecular sieve A-2 and the weight ratio of molecular sieve A-2 to alumina was 8:2, obtaining the catalyst C-2. The bulk ratio of catalyst C-2 was 0.40g/ml.
(6) A method for removing olefin from hydrocarbon oil, specifically:
the catalyst C-2 is respectively contacted with three hydrocarbon oils containing olefin (the specific composition and properties are listed in the following table 1) to carry out the olefin removal reaction, and the reaction conditions comprise: the temperature is 190 ℃, the gauge pressure is 2.5MPa, and the mass space velocity is 3h -1 The results of the reaction for 6 hours are shown in Table 2.
Comparative example 2
A molecular sieve, a catalyst, and a hydrocarbon oil dealkenation reaction were prepared according to the method of example 2, except that, in the step (1), silica sol, sodium aluminate, naOH, hexamethyleneimine, and water were mixed with stirring at 27 ℃ for 3 hours. The acid content of the prepared molecular sieve DA-2 is 0.7mg NH 3 Per 100mg. The bulk ratio of catalyst DC-2 was 0.36g/ml. The results of the 6-hour dealkenation of the hydrocarbon oil are shown in Table 2.
Example 3
(1) Stirring and mixing silica sol, sodium aluminate, naOH, hexamethyleneimine and water for 1h at the temperature of 10 ℃ to prepare a silicon source, an aluminum source, an alkali source, a template agent and water with the molar ratio of 10:0.75:17:3:120, wherein the silicon source is SiO 2 In terms of aluminum source, al is calculated 2 O 3 Calculated as OH as alkali source - And (6) counting.
(2) The mixture is crystallized for 80h at 145 ℃, and then filtered and dried (120 ℃) to obtain a solid product.
(3) Ammonium exchange was carried out in the same manner as in step (3) of example 1.
(4) And roasting the product obtained by ammonium exchange at 490 ℃ for 28h to obtain the molecular sieve A-3.
The XRD pattern and SEM image of the molecular sieve A-3 are respectively similar to those of the molecular sieve A-1, and the molecular sieve A-3 is proved to be MWW molecular sieve and to have a single-layer sheet-like structure.
The acid content of molecular sieve A-3 was found to be 1.3mg NH by analysis 3 100mg, and the molar ratio of silicon to aluminum is 26.
(5) A catalyst was prepared in the same manner as in step (5) in example 1, except that molecular sieve A-1 was replaced with molecular sieve A-3 and the weight ratio of molecular sieve A-3 to alumina was 6:4, obtaining the catalyst C-3. The bulk ratio of catalyst C-3 was 0.39g/ml.
(6) A method for removing olefin from hydrocarbon oil, specifically:
the catalyst C-3 is respectively contacted with three hydrocarbon oils (the specific composition and properties are shown in the following table 1) containing olefin to carry out the olefin removing reaction, and the reaction conditions comprise that: the temperature is 170 ℃, the gauge pressure is 2.5MPa, and the mass space velocity is 15h -1 The results of the 4-hour reaction are shown in Table 2.
Comparative example 3
A molecular sieve, a catalyst, and a hydrocarbon oil dealkenation reaction were prepared according to the method of example 3, except that, in the step (1), silica sol, sodium aluminate, naOH, hexamethyleneimine, and water were mixed with stirring at 25 ℃ for 1 hour. The acid content of the prepared molecular sieve DA-3 is 0.7mg NH 3 Per 100mg. The bulk ratio of catalyst DC-3 was 0.36g/ml. The results of 4 hours deolefination of hydrocarbon oil are shown in Table 2.
Example 4
(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 10:0.7:17:2.5:120, wherein the silicon source is SiO 2 In terms of aluminum source, al is calculated 2 O 3 Calculated as OH as alkali source - And (6) counting.
(2) The mixture is crystallized for 90h at 150 ℃, and then filtered and dried (120 ℃) to obtain a solid product.
(3) Ammonium exchange was carried out in the same manner as in step (3) of example 1.
(4) And roasting the product obtained by ammonium exchange at 500 ℃ for 35 hours to obtain the molecular sieve A-4.
The XRD pattern and SEM image of the molecular sieve A-4 are respectively similar to those of the molecular sieve A-1, and the molecular sieve A-4 is proved to be MWW molecular sieve and to have a single-layer sheet-like structure.
The acid content of molecular sieve A-4 was found to be 1.4mg NH by analysis 3 100mg, and the molar ratio of silicon to aluminum is 28.
(5) A catalyst was prepared in the same manner as in step (5) in example 1, except that molecular sieve A-1 was replaced with molecular sieve A-4 and the weight ratio of molecular sieve A-4 to alumina was 7:3, obtaining the catalyst C-4. The bulk ratio of catalyst C-4 was 0.43g/ml.
(6) A method for removing olefin from hydrocarbon oil, specifically:
the catalyst C-4 is respectively contacted with three hydrocarbon oils containing olefin (the specific composition and properties are listed in the following table 1) to carry out the olefin removal reaction, and the reaction conditions comprise: the temperature is 180 ℃, the gauge pressure is 3.0MPa, and the mass space velocity is 40h -1 The results of the reaction for 10 hours are shown in Table 2.
Example 5
The hydrocarbon oil dealkenation was carried out by preparing a molecular sieve and a catalyst according to the method of example 1 except that SiO was used in the step (1) 2 Silicon source and OH - The molar ratio of the alkali source calculated is 10:10. the XRD pattern and SEM pattern of the obtained molecular sieve A-5 are respectively similar to those of the molecular sieve A-1, and the molecular sieve A-5 is proved to be an MWW molecular sieve and has a single-layer sheet-like structure. As can be seen by analysis, the acid amount of molecular sieve A-5 was 1.0mg NH 3 And/100 mg. The bulk ratio of the obtained catalyst C-5 was 0.38g/ml. The results of the 6-hour dealkenation of the hydrocarbon oil are shown in Table 2.
Example 6
The hydrocarbon oil dealkenation was carried out by preparing a molecular sieve and a catalyst according to the method of example 1 except that SiO was used in the step (1) 2 Silicon source and OH - The molar ratio of the alkali source is 10:20. the XRD pattern and SEM image of the obtained molecular sieve A-6 are respectively similar to those of the molecular sieve A-1, and the molecular sieve A-6 is proved to be MWW molecular sieve and to have a single-layer sheet-like structure. The acid content of molecular sieve A-6 was found by analysis to be 0.9mg NH 3 Per 100mg. The bulk ratio of the obtained catalyst C-6 was 0.38g/ml. The results of the 6-hour dealkenation of the hydrocarbon oil are shown in Table 2.
Example 7
The catalyst C-1 is prepared according to the method of example 1, and the catalyst C-1 is treated under the harsh condition of high space velocity to deactivate the catalyst C-1, which specifically comprises the following steps: at a temperature of 175 ℃ toThe pressure of the gauge pressure meter is 2.5MPa, and the mass space velocity is 60h -1 And the reaction was carried out for 500 hours. And (3) regenerating the deactivated catalyst for 4 hours at the reaction temperature of 500 ℃ under the condition of introducing air. The regenerated catalyst was subjected to the olefin removal reaction according to the step (6) of example 1, and the results of the reaction for 6 hours are shown in Table 2.
TABLE 1
| Hydrocarbon oil No. one | Hydrocarbon oil of number two | Hydrocarbon oil No. three | |
| BI, mg Br/100g oil | 280 | 950 | 3900 |
| Xylene content, wt.% | 45.9 | 28.9 | 6.5 |
| Content of trimethylbenzene,% by weight | 28.7 | 27.6 | 11.2 |
| Content of dimethyl ethylbenzene, wt.% | 9.8 | 16.4 | 21.3 |
| Content of tetramethylbenzene,% by weight | 6.8 | 16.6 | 41.2 |
| Naphthalene content, wt.% | 0.9 | 1.2 | 6.8 |
| Content of other aromatic hydrocarbons and unsaturated olefins,% by weight | 7.9 | 9.3 | 13.0 |
TABLE 2
| BI of Hydrocarbon oil after reaction | BI after reaction of No. two hydrocarbon oils | BI after reaction of No. three Hydrocarbon oils | |
| Raw materials | 280 | 950 | 3900 |
| Example 1 | 35 | 110 | 450 |
| Comparative example 1 | 150 | 480 | 2110 |
| Example 2 | 25 | 90 | 320 |
| Comparative example 2 | 160 | 535 | 2280 |
| Example 3 | 80 | 260 | 1130 |
| Comparative example 3 | 220 | 790 | 3100 |
| Example 4 | 95 | 300 | 1480 |
| Example 5 | 105 | 360 | 1500 |
| Example 6 | 110 | 370 | 1550 |
| Example 7 | 35 | 110 | 455 |
Note: the BI reported in Table 2 is in mg Br per 100g of oil.
The results in table 2 show that the catalyst prepared by using the molecular sieve provided by the invention has higher activity when used in the process of olefin removal reaction of hydrocarbon oil, and the bromine index of the raw material is reduced by at least 60%. In addition, as can be seen from the comparative data of example 1 and example 7, the deactivated catalyst still has better activity after regeneration, which proves that the catalyst provided by the invention has longer service life.
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 various technical features being combined 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 (34)
1. An MWW molecular sieve, characterized in that the acid content of the molecular sieve is not less than 0.9mg NH 3 100mg; the molecular sieve has a single-layer lamellar structure; wherein the acid content of the molecular sieve is measured by ammonia adsorption method, and the acid content of the molecular sieve is measured by ammonia adsorption methodThe method for testing the quantity 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 = (b-a)/a × 100% formula (1);
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 the 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 SiO 2 In terms of aluminum source, al is calculated 2 O 3 Calculated as OH as alkali source - And (6) counting.
2. The molecular sieve of claim 1, wherein the molecular sieve has an acid content of not less than 1mg NH 3 /100mg。
3. The molecular sieve of claim 2, wherein the molecular sieve has an acid content of not less than 1.2mg NH 3 /100mg。
4. The molecular sieve of claim 3, wherein the molecular sieve has an acid amount of 1.2 to 2.5mg NH 3 /100mg。
5. The molecular sieve of any of claims 1-4, wherein the molecular sieve has a silica to alumina molar ratio of 20 to 100:1.
6. the molecular sieve of claim 5, wherein the molecular sieve has a silica to alumina molar ratio of 20 to 50:1.
7. a process for preparing an MWW molecular sieve, wherein the process 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, wherein the silicon source is SiO 2 In terms of aluminum source, al is calculated 2 O 3 Calculated as OH as alkali source - And (6) counting.
8. The production method according to claim 7, wherein the mixing of step (1) is performed at 0 to 10 ℃.
9. The production method according to claim 8, wherein the mixing of step (1) is performed at 2 to 10 ℃.
10. The method of claim 7, wherein the mixing time is 0.1 to 10 hours.
11. The method of claim 10, wherein the mixing time is 0.5-3 hours.
12. The production method according to any one of claims 7 to 11, wherein 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.
13. The production method according to claim 12, wherein 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.
14. The production method according to any one of claims 7 to 11,
the silicon source is an inorganic silicon source;
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 inorganic alkali;
the template agent is at least one selected from ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, hexahydropyridine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine and octadecylamine.
15. The production method according to claim 14, wherein the silicon source is at least one of silica, silica sol, and water glass.
16. The method of claim 15, wherein the silicon source is silica sol and/or water glass.
17. The production method according to claim 14, wherein the alkali source is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and calcium hydroxide.
18. The production method according to claim 17, wherein the alkali source is sodium hydroxide and/or potassium hydroxide.
19. The production method according to any one of claims 7 to 11, wherein the hydrothermal crystallization conditions of step (2) include: the temperature is 100-200 ℃; the time is 5-200h.
20. The preparation method of claim 19, wherein the hydrothermal crystallization conditions of step (2) include: the temperature is 120-190 ℃; the time is 30-120h.
21. The production method according to any one of claims 7 to 11, wherein the conditions for the calcination in the step (3) include: the temperature is 400-600 ℃, and the time is 10-100h.
22. The production method according to any one of claims 7 to 11, further comprising: and (3) before roasting in the step (3), performing ammonium exchange on the solid product obtained in the step (2).
23. An MWW molecular sieve produced by the production process of any one of claims 7 to 22.
24. Use of the MWW molecular sieve of any one of claims 1 to 6 and 23 in the dealkenation of hydrocarbon oils.
25. A catalyst comprising an MWW molecular sieve and a binder, said MWW molecular sieve being the MWW molecular sieve defined in any one of claims 1 to 6 and 23.
26. The catalyst of claim 25, wherein the MWW molecular sieve is present in an amount of 55 to 90 wt%, based on the total amount of catalyst; the content of the binder is 10-45 wt%.
27. The catalyst of claim 26, wherein the MWW molecular sieve is present in an amount of from 60 to 80 wt%, based on the total amount of catalyst; the content of the binder is 20-40 wt%.
28. The catalyst of claim 25, wherein the binder is selected from at least one of alumina, silica, kaolin, bentonite, montmorillonite and sepiolite.
29. The catalyst of claim 25 wherein the bulk ratio of the catalyst is not less than 0.38g/ml.
30. The catalyst of claim 29 wherein the bulk ratio of the catalyst is not less than 0.4g/ml.
31. The catalyst of claim 30 wherein the bulk ratio of the catalyst is from 0.4 to 0.65g/ml.
32. The catalyst of any one of claims 25-31, wherein the catalyst is prepared by a method comprising:
a) Extruding MWW molecular sieve and binder and/or precursor thereof into strips for molding to obtain a molded object;
b) And drying and roasting the formed product.
33. A process for the deolefination of a hydrocarbon oil, the process comprising: contacting a hydrocarbon oil with a catalyst under olefin removal conditions, wherein the catalyst is according to any one of claims 25 to 32.
34. The method of claim 33, wherein the de-olefm conditions comprise: the temperature is 100-250 ℃, the pressure is 1-5MPa and the mass space velocity is 0.5-50h in gauge pressure -1 。
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| CN102008976A (en) * | 2010-11-09 | 2011-04-13 | 中国海洋石油总公司 | Method for preparing olefin-removing catalyst |
| CN103771435A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Method for synthesis of MCM-22 molecular sieve |
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| CN1654330A (en) * | 2005-01-24 | 2005-08-17 | 复旦大学 | Method for preparing aluminium-containing MCM-41 inter-aperture molecular screen using metakaolin as raw material |
| CN101798525A (en) * | 2009-02-06 | 2010-08-11 | 中国石油化工股份有限公司 | Oxidation sweetening method for diesel oil |
| CN102008976A (en) * | 2010-11-09 | 2011-04-13 | 中国海洋石油总公司 | Method for preparing olefin-removing catalyst |
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