CN110560151A - Molecular sieve solid acid catalyst, preparation method and application thereof - Google Patents

Molecular sieve solid acid catalyst, preparation method and application thereof Download PDF

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Publication number
CN110560151A
CN110560151A CN201910872857.5A CN201910872857A CN110560151A CN 110560151 A CN110560151 A CN 110560151A CN 201910872857 A CN201910872857 A CN 201910872857A CN 110560151 A CN110560151 A CN 110560151A
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molecular sieve
acid catalyst
solid acid
ethylene
ethanol
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裴仁彦
夏春晖
吕新新
赵文广
杨冬荣
任晓光
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Yanchang Zhongke (dalian) Energy Technology Co Ltd
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Yanchang Zhongke (dalian) Energy Technology Co Ltd
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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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The application discloses a molecular sieve solid acid catalyst, wherein the carrier of the molecular sieve solid acid catalyst is made of macroporous Al2O3And an HMOR molecular sieve, wherein the carrier is loaded with P. The molecular sieve solid acid catalyst has the advantages of low reaction temperature, high catalytic activity and selectivity and good stability in the preparation of ethylene by ethanol dehydration. The application also discloses a preparation method of the molecular sieve solid acid catalyst, which is simple in process and obvious in effect and solves the problems of high reaction temperature, low airspeed, high energy consumption and the like in the process of preparing ethylene by ethanol dehydration at present.

Description

Molecular sieve solid acid catalyst, preparation method and application thereof
Technical Field
The application relates to a molecular sieve solid acid catalyst, a preparation method and application thereof, in particular to a molecular sieve solid acid catalyst for preparing ethylene by ethanol dehydration, a preparation method and application thereof, and belongs to the field of catalytic synthesis.
Background
The ethylene industry is the core of the petrochemical industry, and ethylene products account for more than 75% of petrochemical products and are one of the important marks for measuring the national petrochemical development level. The downstream derivatives produced by using ethylene as raw material mainly include polyethylene, polyvinyl chloride, styrene, polystyrene and ethylene oxide.
improving the ethylene production capacity is an important way for petrochemical technology and product innovation, the global ethylene production capacity is expected to reach 1.49 hundred million tons by 2022, the newly increased ethylene production capacity in the middle east region is expected to exceed 800 ten thousand tons, the newly increased ethylene production capacity in North America is expected to be about 1100 ten thousand tons, the newly increased ethylene production capacity in the Asia-Pacific region is expected to exceed 1500 ten thousand tons, and the Brazil and Russian production capacities are also greatly improved. The global ethylene industry layout is still sub-pacific, north american. Unlike north america and middle east where export is the goal, the new capacity increase in asia-pacific region is to meet their own market needs.
Since the 21 st century, the ethylene industry in China has been greatly developed in terms of production technology, equipment scale and single furnace capacity, and has become the second largest ethylene producing country second only to the United states. The localization rate in the aspect of ethylene production equipment is over 70 percent, millions of tons of ethylene equipment can be built by self, and the ethylene industry is in the advanced world line. However, from the market of China, the shortage of high-quality ethylene raw materials is one of the bottlenecks in improving the comprehensive competitiveness of the ethylene industry of China. Although ethylene enterprises develop ethylene raw materials in a diversified way by continuously excavating and submerging internal raw materials and reasonably purchasing the raw materials externally, the supply and demand contradiction of the ethylene raw materials is relieved to a certain extent, but the supply of the ethylene raw materials still has huge gaps. Domestic ethylene capacity cannot completely meet the demand of the domestic ethylene production, and the domestic ethylene industry still needs to be vigorously developed.
several companies have been available at home and abroad to provide a technology for producing ethylene and its by-products from ethanol. The technical key point of the process for preparing the ethylene by catalyzing and dehydrating the ethanol is to select a proper catalyst. There are many reported ethanol dehydration catalysts, and the main catalysts with industrial application value are active alumina catalysts and molecular sieve catalysts. In the last 80 th century, Syndol's catalyst was developed by Halcon corporation of America, and the catalyst has good overall performance, but the catalyst has strict requirements on reaction conditions, high reaction temperature and low space velocity, and the overall energy consumption is high. Pan-Dome et al of the university of south-opening describe in patent CN1009363B a molecular sieve type catalyst with the code NKC-03A, which is not very stable at temperatures below 300 ℃.
Therefore, the development of a catalyst for preparing ethylene by ethanol dehydration, which has low reaction temperature, high activity and selectivity and good stability, is an important research direction in the current catalyst development.
disclosure of Invention
According to one aspect of the application, a molecular sieve solid acid catalyst is provided, which has low reaction temperature, high catalytic activity and selectivity and good stability for preparing ethylene by ethanol dehydration.
the molecular sieve solid acid catalyst is characterized in that the carrier of the molecular sieve solid acid catalyst is made of macroporous Al2O3And an HMOR molecular sieve, wherein the carrier is loaded with P.
Optionally, the molecular sieve solid acid catalyst contains 2-15% of P.
Optionally, the carrier has macropores Al2O3The content is 15-75 wt%.
Optionally, the carrier has macropores Al2O3The pseudoboehmite with the pore volume of 0.4ml/g produced by Shandong Haiming.
According to another aspect of the application, the preparation method of the molecular sieve solid acid catalyst is provided, the method is simple in process and obvious in effect, and the problems of high reaction temperature, low space velocity, high energy consumption and the like in the existing process of preparing ethylene by ethanol dehydration are well solved.
A process for the preparation of the molecular sieve catalyst, the process at least comprising the steps of:
(1) Preparing an HMOR molecular sieve;
(2) Obtaining a solution containing a source of P;
(3) Will consist of macroporous Al2O3And (3) adding a carrier consisting of an HMOR molecular sieve into the solution obtained in the step (2), drying and roasting to obtain the molecular sieve solid acid catalyst.
Optionally, the method for preparing the HMOR molecular sieve in step (1) comprises at least the following steps:
a. Mixing a silicon source and an alkali source to obtain a mixed solution M;
b. Adding an aluminum source solution into the mixed solution M to obtain a mixed solution N;
c. adding a template agent into the mixed solution N, and crystallizing to obtain solid S;
d. And carrying out ammonium ion exchange on the solid S to obtain the HMOR molecular sieve.
Preferably, the silicon-aluminum molecular ratio of the HMOR molecular sieve is 10-40.
Preferably, the silicon source is selected from at least one of sodium silicate, silica sol and water glass.
preferably, the alkali source is selected from at least one of sodium hydroxide and potassium hydroxide.
Preferably, the aluminum source is selected from at least one of aluminum sulfate, aluminum nitrate, aluminum hydroxide, and aluminum isopropoxide.
Preferably, the template agent is at least one selected from tetraethylammonium hydroxide, hexadecyltrimethylammonium hydroxide and triethylamine.
Preferably, the solid S is subjected to ammonium ion exchange using at least one of ammonium chloride, ammonium nitrate, ammonium sulfate.
Optionally, the source of P is at least one of ammonium phosphate, ammonium hydrogen phosphate.
Preferably, the mass fraction of the ammonium phosphate is 2-15%.
Preferably, the source of P is ammonium phosphate.
alternatively, the HMOR molecular sieve is prepared as follows:
a. mixing sodium silicate, silica sol or water glass with a sodium hydroxide solution;
b. Preparing at least one of aluminum sulfate, aluminum nitrate, aluminum hydroxide and aluminum isopropoxide into an aqueous solution;
c. Adding the water solution prepared by the step b into the step a;
d. Adding at least one of tetraethylammonium hydroxide, hexadecyltrimethylammonium hydroxide and triethylamine to the solution c;
e. Stirring for 10-120 min, heating to 130-180 ℃, and crystallizing at constant temperature for 10-60 h;
f. Washing and filtering the solid obtained in the step e;
g. And (3) performing ammonium exchange on the solid obtained in the step (f) by using at least one of ammonium chloride, ammonium nitrate and ammonium sulfate to obtain the HMOR molecular sieve, wherein the molecular ratio of silicon to aluminum is 10-40.
Optionally, the step (3) is performed by using macroporous Al2O3The preparation method of the carrier consisting of the HMOR molecular sieve comprises the following steps:
a. Grinding the HMOR molecular sieve to be more than 180 meshes, adding pseudo-boehmite with the pore volume of 0.4ml/g, and then adding sesbania powder;
b. Preparing a nitric acid solution;
c. Adding the prepared nitric acid solution of the step b into the step a;
d. C, uniformly mixing the materials obtained in the step c, extruding and forming;
e. Drying and roasting to obtain the macroporous Al2O3and a carrier consisting of HMOR molecular sieve.
optionally, in step (3), the drying conditions are: and drying at 110-200 ℃.
Optionally, the roasting condition is that roasting is carried out for 3-6 hours at 380-600 ℃.
Optionally, the upper limit of the firing temperature is selected from 600 ℃, 540 ℃, 500 ℃ or 450 ℃, and the lower limit is selected from 380 ℃, 420 ℃, 450 ℃ or 500 ℃.
according to still another aspect of the application, the application of at least one of the molecular sieve solid acid catalyst and the molecular sieve solid acid catalyst prepared by the method in the reaction for preparing ethylene by ethanol dehydration is provided.
According to yet another aspect of the present application, there is provided a process for the dehydration of ethanol to produce ethylene, using a catalyst as described above, in a fixed bed reactor from N2After purging, the ethanol water solution enters a catalyst layer of the reactor through a double-plunger pump, and the conversion rate of ethanol reaches 9 under the condition that the central temperature of a bed layer is 220-350 DEG C9.8 percent and the selectivity of ethylene reaches 99.2 percent. Under the condition of unchanged test conditions, the catalyst is continuously operated for 1000 hours, the conversion rate of the ethanol is still 99.8 percent, and the selectivity of the ethylene is 99.1 percent.
The method for preparing ethylene by ethanol dehydration is characterized in that raw materials containing ethanol aqueous solution are introduced into a reactor filled with a molecular sieve solid acid catalyst for contact reaction to obtain ethylene;
The molecular sieve catalyst is at least one selected from the molecular sieve solid acid catalyst and the molecular sieve solid acid catalyst prepared by the method.
optionally, the reactor is a fixed bed reactor.
Optionally, the reaction temperature is 220-350 ℃.
Alternatively, the upper limit of the reaction temperature is selected from 350 ℃, 300 ℃, 290 ℃ or 260 ℃, and the lower limit is selected from 220 ℃, 240 ℃, 260 ℃ or 290 ℃.
Optionally, the aqueous ethanol solution is a high concentration aqueous ethanol solution.
Optionally, the mass concentration of the ethanol aqueous solution is greater than 50% and less than 99.7%.
optionally, the reaction space velocity is 1.0-3.5 h-1。
Optionally, the method further comprises feeding N into the reactor2And blowing the molecular sieve solid acid catalyst for 1-2 hours at the temperature of 350-450 ℃.
Optionally, the mass concentration of the ethanol water solution is 50-99.7%; the reaction space velocity is 1.0-3.5 h-1。
Optionally, the introducing pressure of the ethanol water solution is 0.1-0.4 MPa.
preferably, the introducing pressure of the ethanol aqueous solution is 0.3 MPa.
the beneficial effects that this application can produce include:
1) The molecular sieve catalyst provided by the application has a certain amount of macroporous Al2O3Increasing the medium-strong acid quantity on the surface of the catalyst, increasing the active sites of the medium-strong acid exposed on the surface of the molecular sieve catalyst, and inhibiting the generation of ethylenefurther polymerization side reactions. Therefore, the molecular sieve catalyst can better convert ethanol into ethylene in the reaction of preparing ethylene by ethanol dehydration. Adding proper amount of macroporous Al2O3The HMOR molecular sieve of (a) produces a catalyst containing more Al than the complete use of HMOR or the HMOR2O3the catalyst prepared by the molecular sieve has better ethanol dehydration performance. The molecular sieve catalyst provided by the application can be suitable for ethanol with different concentrations.
2) According to the preparation method of the molecular sieve catalyst, a proper amount of P is impregnated, other modification treatment is not needed, and the conversion rate of ethanol at 220 ℃ can reach 99%. The reaction temperature is low, and the carbon deposition rate of the catalyst can be reduced, so that the service life of the catalyst is prolonged.
3) The method for preparing ethylene by ethanol dehydration has the advantages of simple process and obvious effect, and better solves the problems of high reaction temperature, low airspeed, high energy consumption and the like in the existing process of preparing ethylene by ethanol dehydration.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of the present application were all purchased commercially, wherein: al (Al)2O3Is obtained from pseudoboehmite purchased from Shandong Haiming.
the conversion, selectivity, in the examples of the present application were calculated as follows:
Conversion rate of ethanol:
Ethylene selectivity:
In the formula, XEtohConversion of ethanol, NEtoh,inThe number of moles of ethanol introduced into the reactor, NEtoh,outMoles of unreacted ethanol, SEthyleneselectivity to ethylene, NEthyleneThe moles of ethylene formed by the reaction (equal to the moles of ethanol consumed to form ethylene).
according to one embodiment of the application, a solid acid molecular sieve catalyst with low reaction temperature, high catalytic activity and selectivity and good stability is provided. Will consist of Al2O3And HMOR molecular sieve into solution containing P to make the carrier surface load with P. And drying the reactant at 110-200 ℃, and roasting at 380-600 ℃ for 3h to obtain the catalyst.
Example 1
Weighing 17g of aluminum sulfate to prepare a solution, preparing 500g of sodium silicate and 15g of sodium hydroxide to prepare a solution, adding the solution into the aluminum sulfate solution, and adding tetraethylammonium hydroxide to obtain a sol containing SiO2：Al2O3：Na2O：TEAOH：H2O15: 1: 0.5: 2: 20. stirring for 120min, heating to 170 deg.C, crystallizing at constant temperature for 48h, washing the obtained solid, and filtering; preparing 1mol/L ammonium chloride solution, carrying out ammonium ion exchange on the solid obtained by filtering, drying at 150 ℃, and roasting at 500 ℃ for 4h to obtain the HMOR molecular sieve A with the silicon-aluminum ratio of 15.
Example 2
Weighing 11g of aluminum nitrate to prepare a solution, mixing 13g of sodium hydroxide with 500g of silica sol solution, adding the mixture into the aluminum nitrate solution, and then adding hexadecyl trimethyl ammonium hydroxide, wherein the sol consists of SiO2：Al2O3：Na2O：CTAOH：H2o25: 1: 0.5: 3: 30. stirring for 120min, heating to 180 deg.C, crystallizing at constant temperature for 48h, washing the obtained solid, and filtering; preparing 1mol/L ammonium nitrate solution, carrying out ammonium ion exchange on the solid obtained by filtering, drying at 150 ℃, and roasting at 500 ℃ for 4h to obtain the HMOR molecular sieve B with the silicon-aluminum ratio of 25.
Example 3
weighingPreparing 11g of aluminum nitrate into a solution, mixing 19g of sodium hydroxide with 800g of silica sol solution, adding the mixture into the aluminum nitrate solution, and adding tetraethylammonium hydroxide, wherein the sol consists of SiO2：Al2O3：Na2O：TEAOH：H2O-40: 1: 0.7: 3: 50. stirring for 120min, heating to 190 deg.C, crystallizing at constant temperature for 48h, washing the obtained solid, and filtering; preparing 1mol/L ammonium chloride solution, carrying out ammonium ion exchange on the solid obtained by filtering, drying at 150 ℃, and roasting at 500 ℃ for 4h to obtain the HMOR molecular sieve C with the silicon-aluminum ratio of 40.
Example 4
Preparing an ammonium phosphate solution with the mass fraction of l00ml being 8 percent, placing the ammonium phosphate solution into a flask provided with a thermometer and a stirrer, and then adding macroporous Al2O3And HMOR molecular sieve, wherein Al is 75g2O3The mass fraction of (b) is 15%, stirring at room temperature for 3.5h to carry out surface loading reaction. And after the reaction is finished, controlling the temperature to be 120 ℃ for drying, and roasting at 540 ℃ for 3h to obtain the molecular sieve catalyst A suitable for preparing ethylene by ethanol dehydration.
Example 5
Preparing 3 percent ammonium phosphate solution of l00ml mass fraction, placing the solution in a flask provided with a thermometer and a stirrer, and then adding macroporous Al2O3And HMOR molecular sieve, wherein Al is present in an amount of 75g2O3The mass fraction of (b) is 45%, stirring at room temperature for 3h to carry out surface loading reaction. And after the reaction is finished, controlling the temperature to be 150 ℃ for drying, and roasting at 450 ℃ for 3h to obtain the molecular sieve catalyst B suitable for preparing ethylene by ethanol dehydration.
Example 6
Preparing an ammonium phosphate solution with the mass fraction of l00ml being 12 percent, placing the ammonium phosphate solution into a flask provided with a thermometer and a stirrer, and then adding macroporous Al2O3And HMOR molecular sieve, wherein Al is present in an amount of 75g2O3The mass fraction of (b) is 65%, stirring at room temperature for 4h to carry out surface loading reaction. After the reaction is finished, the reaction mixture is dried at the temperature of 150 ℃ and roasted at the temperature of 600 DEG CAnd 3h, obtaining the molecular sieve catalyst C suitable for preparing ethylene by ethanol dehydration.
Example 7
the molecular sieve catalyst A prepared in the example 4 is applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process is as follows: filling the molecular sieve catalyst A into a fixed bed reactor, and then introducing N into the fixed bed reactor2Purging the molecular sieve catalyst A for 2h at a temperature of 400 ℃; after purging is finished, introducing an ethanol water solution with the mass concentration of 50%, and performing ethanol dehydration reaction at the central temperature of a bed layer of the fixed bed reactor of 240 ℃ to obtain ethylene; the reaction space velocity is 1.5h-1the pressure of the ethanol aqueous solution was 0.3 MPa. The fixed bed reactor is a stainless steel fixed bed reaction tube with phi of 18 multiplied by 500mm, and the filling volume of the catalyst is 10 ml.
Example 8
The molecular sieve catalyst A prepared in the example 4 is applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process is as follows: filling the molecular sieve catalyst A into a fixed bed reactor, and then introducing N into the fixed bed reactor2Purging the molecular sieve catalyst A for 2h at a temperature of 400 ℃; after purging is finished, introducing an ethanol aqueous solution with the mass concentration of 70%, and performing ethanol dehydration reaction at the central temperature of a bed layer of the fixed bed reactor of 240 ℃ to obtain ethylene; the reaction space velocity is 3.5h-1the pressure of the ethanol aqueous solution was 0.3 MPa.
Example 9
the molecular sieve catalyst A prepared in the example 4 is applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process is as follows: filling the molecular sieve catalyst A into a fixed bed reactor, and then introducing N into the fixed bed reactor2Purging the molecular sieve catalyst A for 2h at a temperature of 400 ℃; after purging is finished, introducing an absolute ethyl alcohol solution with the mass concentration of 99.7%, and performing an ethyl alcohol dehydration reaction at the central temperature of a bed layer of the fixed bed reactor of 240 ℃ to obtain ethylene; the reaction space velocity is 1h-1the pressure of the ethanol aqueous solution was 0.3 MPa.
example 10
The molecular sieve catalyst A prepared in the example 4 is applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process is as follows: filling the molecular sieve catalyst A into a fixed bed reactor, and then introducing N into the fixed bed reactor2purging the molecular sieve catalyst A for 2h at a temperature of 400 ℃; after purging is finished, introducing an absolute ethyl alcohol solution with the mass concentration of 99.7%, and performing an ethyl alcohol dehydration reaction at the central temperature of a bed layer of the fixed bed reactor of 220 ℃ to obtain ethylene; the reaction space velocity is 1.5h-1the pressure of the ethanol aqueous solution was 0.3 MPa.
Example 11
the molecular sieve catalyst A prepared in the example 4 is applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process is as follows: filling the molecular sieve catalyst A into a fixed bed reactor, and then introducing N into the fixed bed reactor2Purging the molecular sieve catalyst A for 2h at a temperature of 400 ℃; after purging is finished, introducing an absolute ethyl alcohol solution with the mass concentration of 99.7%, and performing an ethyl alcohol dehydration reaction at the central temperature of a bed layer of the fixed bed reactor of 290 ℃ to obtain ethylene; the reaction space velocity is 1.5h-1the pressure of the ethanol aqueous solution was 0.3 MPa.
example 12
The molecular sieve catalyst A prepared in the example 4 is applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process is as follows: filling the molecular sieve catalyst A into a fixed bed reactor, and then introducing N into the fixed bed reactor2Purging the molecular sieve catalyst A for 2h at a temperature of 400 ℃; after purging is finished, introducing an absolute ethyl alcohol solution with the mass concentration of 99.7%, and performing an ethyl alcohol dehydration reaction at the central temperature of a bed layer of the fixed bed reactor of 350 ℃ to obtain ethylene; the reaction space velocity is 1.5h-1the pressure of the ethanol aqueous solution was 0.3 MPa.
Example 13
The molecular sieve catalyst B prepared in example 5 is applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process is as follows: filling the molecular sieve catalyst B into a fixed bed reactor, and then introducing N into the fixed bed reactor2Purging the molecular sieve catalyst for 2h at the temperature of 400 ℃; after purging is finished, introducing an absolute ethyl alcohol solution with the mass concentration of 99.7%, and performing an ethyl alcohol dehydration reaction at the central temperature of a bed layer of the fixed bed reactor of 260 ℃ to obtain ethylene; the reaction space velocity is 1.5h-1the pressure of the ethanol aqueous solution was 0.3 MPa.
Example 14
The molecular sieve catalyst C prepared in example 6 was applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process was: filling the molecular sieve catalyst C in a fixed bed reactor, and then introducing N into the fixed bed reactor2Purging the molecular sieve catalyst for 2h at the temperature of 400 ℃; after purging is finished, introducing an absolute ethyl alcohol solution with the mass concentration of 99.7%, and performing an ethyl alcohol dehydration reaction at the central temperature of a bed layer of the fixed bed reactor of 260 ℃ to obtain ethylene; the reaction space velocity is 1.5h-1The pressure of the ethanol aqueous solution was 0.3 MPa.
Comparative example 1
In the comparative example, HMOR molecular sieve is completely used as a carrier, 8 mass percent of l00ml ammonium phosphate solution is placed in a flask provided with a thermometer and a stirrer, HMOR75g is added, and the mixture is stirred for 3 hours at room temperature to carry out surface loading reaction. And after the reaction is finished, controlling the temperature to be 120 ℃ for drying, and roasting at 540 ℃ for 3h to obtain the catalyst X.
Comparative example 2
In this comparative example, the alloy is composed of macroporous Al2O3And a carrier prepared from HMOR molecular sieve, wherein Al is2O380% by mass, taking an ammonium phosphate solution with the mass fraction of l00ml of 8%, placing the ammonium phosphate solution in a flask with a thermometer and a stirrer, and adding Al2O375g of a carrier with the mass fraction of 80 percent is stirred for 4 hours at room temperature to carry out surface loading reaction. Reaction junctionAnd after that, controlling the temperature to be 120 ℃ for drying, and roasting at 540 ℃ for 3h to obtain the catalyst Y.
Comparative example 3
In the comparative example, 3% by mass of H3PO4Placing in a flask equipped with thermometer and stirrer, adding 1.2g ammonium metavanadate powder, stirring to dissolve and mix completely, adding macroporous Al2O3And HMOR molecular sieve, wherein Al is present in an amount of 75g2O3The mass fraction of (b) is 45%, stirring at room temperature for 4h to carry out surface loading reaction. And after the reaction is finished, controlling the temperature to be 120 ℃ for drying, and roasting at 540 ℃ for 3h to obtain the catalyst Z.
Comparative example 4
The catalyst X prepared in comparative example 1 was used in the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process was the same as in example 7.
comparative example 5
The catalyst Y prepared in comparative example 2 was used in the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process was the same as in example 7.
Comparative example 6
the catalyst Z prepared in the comparative example 3 is applied to the reaction for preparing ethylene by ethanol dehydration, and the specific reaction process is the same as that of the example 8.
The results of evaluating the performance of the catalysts of examples 7 to 14 and comparative examples 4, 5 and 6 are shown in Table 1.
TABLE 1 evaluation results of catalysts of examples 7 to 14 and comparative examples 3 and 4
As shown by the results of the performance evaluation of the catalysts in Table 1, the catalysts A in examples 7 to 9 have ethanol mass concentration of 50-99.7% and ethanol solution airspeed of 1.0-3.5 h-1The ethanol conversion and the ethylene selectivity are stable within the range of (1). The catalyst has strong adaptability to the concentration of the raw material ethanol and the airspeed of the raw material liquid. Examples 9 to 12, catalystsAt 220 ℃, the conversion rate of the ethanol is more than 99 percent; when the temperature reaches 240 ℃, the conversion rate of the ethanol reaches 99.8 percent, and the selectivity of the ethylene reaches 99.2 percent. Examples 13 and 14 show that the effect is preferable when the amount of P to be impregnated is 12%. Through comparative example 4 and comparative example 5, the method shows that the strong acid active center in the surface of the catalyst is properly increased, and the performance of the ethanol dehydration catalyst is favorably and better improved. By comparative example 6, it is shown that the catalyst of the present application supporting only P can achieve catalyst performance similar to that of the catalyst supporting P, V at the same time.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The molecular sieve solid acid catalyst is characterized in that the carrier of the molecular sieve solid acid catalyst is made of macroporous Al2O3And an HMOR molecular sieve, wherein the carrier is loaded with P.
2. The molecular sieve solid acid catalyst of claim 1, wherein the molecular sieve solid acid catalyst comprises 2-15% P;
Macroporous Al in the carrier2O3The content is 15-75 wt%.
3. A method of preparing the molecular sieve solid acid catalyst of claim 1 or 2, characterized in that the method comprises at least the steps of:
(1) Preparing an HMOR molecular sieve;
(2) obtaining a solution containing a source of P;
(3) Will consist of macroporous Al2O3Adding a carrier consisting of HMOR molecular sieve into the solution obtained in the step (2), drying and roasting to obtain the molecular sievea solid acid catalyst.
4. The process according to claim 3, wherein the process for the preparation of HMOR molecular sieve in step (1) comprises at least the following steps:
a. Mixing a silicon source and an alkali source to obtain a mixed solution M;
b. Adding an aluminum source solution into the mixed solution M to obtain a mixed solution N;
c. adding a template agent into the mixed solution N, and crystallizing to obtain solid S;
d. Performing ammonium ion exchange on the solid S to obtain the HMOR molecular sieve;
Preferably, the silicon-aluminum molecular ratio of the HMOR molecular sieve is 10-40;
preferably, the silicon source is selected from at least one of sodium silicate, silica sol and water glass;
Preferably, the alkali source is selected from at least one of sodium hydroxide and potassium hydroxide;
Preferably, the aluminum source is selected from at least one of aluminum sulfate, aluminum nitrate, aluminum hydroxide, and aluminum isopropoxide;
Preferably, the template agent is selected from at least one of tetraethylammonium hydroxide, hexadecyltrimethylammonium hydroxide and triethylamine;
Preferably, the solid S is subjected to ammonium ion exchange using at least one of ammonium chloride, ammonium nitrate, ammonium sulfate.
5. The method of claim 3 or 4, wherein the source of P is at least one of ammonium phosphate, ammonium hydrogen phosphate;
Preferably, the mass fraction of the P source is 2-15%.
6. The method of claim 3, wherein the Al is a macroporous Al2O3And the mass ratio of the carrier consisting of the HMOR molecular sieve to the P source is 50-5: 1;
preferably, the source of P is ammonium phosphate.
7. The method according to claim 3, wherein in the step (3), the drying conditions are as follows: drying at 110-200 ℃;
The roasting condition is that roasting is carried out for 3-6 hours at 380-600 ℃.
8. Use of at least one of the molecular sieve solid acid catalyst of any one of claims 1-2, the molecular sieve solid acid catalyst prepared by the method of any one of claims 3-7 in a reaction for the dehydration of ethanol to produce ethylene.
9. The method for preparing ethylene by ethanol dehydration is characterized in that raw materials containing ethanol aqueous solution are introduced into a reactor filled with a molecular sieve solid acid catalyst for contact reaction to obtain ethylene;
the molecular sieve solid acid catalyst is selected from at least one of the molecular sieve solid acid catalyst of any one of claims 1-2, the molecular sieve solid acid catalyst prepared by the method of any one of claims 3-7.
10. The method for preparing ethylene by dehydrating ethanol according to claim 9, wherein the reactor is a fixed bed reactor;
The reaction temperature is 220-350 ℃;
the mass concentration of the ethanol water solution is 50-99.7%;
The reaction space velocity is 1.0-3.5 h-1。
CN201910872857.5A 2019-09-16 2019-09-16 Molecular sieve solid acid catalyst, preparation method and application thereof Pending CN110560151A (en)

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Application publication date: 20191213