CN102078822A - Method for preparing catalyst for preparing low carbon olefin by using methanol - Google Patents
Method for preparing catalyst for preparing low carbon olefin by using methanol Download PDFInfo
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention discloses a method for preparing a catalyst for preparing low carbon olefin by using methanol, which comprises the following steps of: reacting 85 mass percent of phosphoric acid with ethyl orthosilicate, cobalt source, aluminum source, diethylenetriamine and distilled water under the conditions that the pH is 5.0 to 7.0 and the temperature is 160 to 220 DEG C to form a CoSAPO-101 molecular sieve, grinding the molecular sieve into fine powder, and roasting the fine powder, adhesive and mixed solution containing nitric acid for 5 to 12 hours at the temperature of between 350 and 480 DEG C to form the catalyst. The catalyst prepared by the method has better catalytic performance, the selectivity of ethylene in the reaction of preparing the low carbon olefin by using the methanol can be stabilized at over 50 percent, and the conversion rate of the methanol can reach over 90 percent.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of catalyst that is used for preparing light olefins from methanol.
Background technology
Low-carbon alkene such as ethene, propylene is an important chemical material.Low-carbon alkenes such as present ethene, propylene more than 80% all derive from PETROLEUM PROCESSING.But, reduced the economic benefit of manufacturing enterprise because rise in oil price and resource reserve problem cause ethene, propylene feedstocks cost to raise.By methyl alcohol or dimethyl ether is that catalytic material is produced low-carbon alkene and become the novel technology of producing low-carbon alkene that is hopeful to replace petroleum path most.The synthesis technique of methyl alcohol is quite ripe, and raw material sources are abundant, can coal, to be that raw material is synthetic obtain natural gas.Seeking appropriate catalyst, is the key point that methanol conversion is produced alkene.Mobil company once adopted the ZSM-5 molecular sieve as the preparing light olefins from methanol catalyst of (being called for short MTO), but this molecular sieve is lower to the selectivity of ethene and propylene, and produced accessory substances such as more aromatic hydrocarbons, paraffin, so do not realize industrialization.U.S. Pat 4440871 has been reported the novel SAPO series molecular sieve of U.S. carbon compound company (UCC) exploitation, and wherein SAPO-34 shows the catalytic performance good to MTO.Both at home and abroad the expert has carried out the research of a series of synthetic and modification to ZSM series molecular sieve and SAPO series molecular sieve subsequently, as publication number is the Chinese patent of CN92106213.3, CN1268591C, U.S.P4499327 etc., and its catalytic performance that is used for producing light olefins checked and rated, but still there is easy inactivation in these molecular sieve catalysts, selectivity of light olefin is on the low side, problems such as cost height.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned catalyst, and a kind of feed stock conversion height when being used for methyl alcohol and preparing low-carbon alkene, Preparation of catalysts method that selectivity of product is high are provided.
Solving the problems of the technologies described above the technical scheme that is adopted is made up of following step:
1, synthetic CoSAPO-101 molecular sieve
With mass fraction 85% phosphoric acid and ethyl orthosilicate, the cobalt source, the aluminium source, diethylenetriamine, distilled water is pressed P element and Si element, the Co element, the Al element, diethylenetriamine, the mol ratio of distilled water is 1: 0.02～0.1: 0.25～0.6: 0.3～0.9: 0.5～1.0: 40～100 to mix, regulating pH with acetic acid or ammoniacal liquor is 5.0～7.0, the liner of packing into is in the withstand voltage reactor of polytetrafluoroethylene (PTFE), reactor is put into baking oven, be warming up to 160～220 ℃, isothermal reaction 4～72 hours, cool, filter, crystal washs 2～5 times with distilled water, put into 60～100 ℃ of dryings of baking oven 5～10 hours, and be prepared into the CoSAPO-101 molecular sieve.
Above-mentioned cobalt source is cobalt acetate or cobaltous sulfate or cobalt chloride; The aluminium source is nano-aluminum hydroxide or boehmite.
2, preparation catalyst
The CoSAPO-101 molecular sieve is put into ball mill grind to form fine powder below 400 orders, obtain CoSAPO-101 molecular sieve fine powder; With mass fraction is that 4% aqueous solution of nitric acid or two oxalic acid hydrates and mass fraction are that the mass ratio of 4% aqueous solution of nitric acid is 1: 5～13 mixed liquor or sodium metasilicate and two oxalic acid hydrates, mass fraction is that the mass ratio of 4% aqueous solution of nitric acid is that 1: 1～3: 10～25 mixed liquor joins in the binding agent, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of binding agent are 1: 1～3, stir, dropping ammonia is regulated pH to 6～7, add CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and binding agent is 1: 0.5～3, stir, knead into the ball that particle diameter is 3～6mm, 350～480 ℃ of roastings 5～12 hours, naturally be chilled to room temperature, be prepared into catalyst.
Above-mentioned binding agent is any one in aluminium oxide, nano-aluminum hydroxide, boehmite, silica or the magnesia.
In the synthetic CoSAPO-101 molecular sieve step 1 of the present invention, mass fraction is that the optimum mole ratio of P element and Si element in 85% phosphoric acid and ethyl orthosilicate, cobalt source, aluminium source, diethylenetriamine, the distilled water, Co element, Al element, diethylenetriamine, distilled water is 1: 0.06: 0.36: 0.57: 0.73: 67.
In the synthetic CoSAPO-101 molecular sieve step 1 of the present invention, reaction temperature the best is 180 ℃, and reaction time the best is 24 hours.
In the preparation catalyst step 2 of the present invention, the optimum quality ratio of CoSAPO-101 molecular sieve fine powder and binding agent is 1: 2.
Cobalt of the present invention source the best is a cobalt acetate.
Aluminium of the present invention source the best is a boehmite.
Binding agent the best of the present invention is a nano-aluminum hydroxide.
The catalyst of the present invention's preparation has catalytic performance preferably, and selectivity of ethylene can be stabilized in more than 50% in the reaction for preparing light olefins from methanol, and conversion of methanol can reach more than 90%.
Description of drawings
Fig. 1 is the catalyst reaction device schematic diagram of preparing light olefins from methanol.
The specific embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Embodiment 1
1, synthetic CoSAPO-101 molecular sieve
Get the 17.64g mass fraction and be 85% phosphoric acid, 1.91g ethyl orthosilicate, 13.72g cobalt acetate, 5.23g boehmite, 11.52g diethylenetriamine, 184.52g distilled water mixes, mass fraction is 85% phosphoric acid and ethyl orthosilicate, cobalt acetate, boehmite, diethylenetriamine, the mol ratio of distilled water is 1: 0.06: 0.36: 0.57: 0.73: 67, regulating pH with acetic acid or ammoniacal liquor is 6.6, the liner of packing into is in the withstand voltage reactor of polytetrafluoroethylene (PTFE), reactor is put into baking oven, be warming up to 180 ℃, isothermal reaction 24 hours, cool, filter, crystal washs 2～5 times with distilled water, put into 95 ℃ of dryings of baking oven 7 hours, and be prepared into the CoSAPO-101 molecular sieve.
2, preparation catalyst
The CoSAPO-101 molecular sieve is put into ball mill grind to form the following fine powder of 400 orders, obtain CoSAPO-101 molecular sieve fine powder; With the 6.4g mass fraction is that 4% aqueous solution of nitric acid joins in the 8.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 1.25, stir, dropping ammonia is regulated pH to 6～7, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 2, stir, knead into the ball that particle diameter is 3～6mm, 400 ℃ of roastings 12 hours, take off diethylenetriamine, moisture and nitric acid, be chilled to room temperature naturally, be prepared into catalyst.
Embodiment 2
In the preparation catalyst step 2 of present embodiment, with the 3.2g mass fraction is that 4% aqueous solution of nitric acid joins in the 4.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 1.25, stir, dropping ammonia is regulated pH to 6～7, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 1, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine is taken off in 400 ℃ of roastings 12 hours, moisture and nitric acid are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 3
In the preparation catalyst step 2 of present embodiment, with the 9.6g mass fraction is that 4% aqueous solution of nitric acid joins in the 12.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 1.25, stir, dropping ammonia is regulated pH to 6～7, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 3, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine is taken off in 400 ℃ of roastings 12 hours, moisture and nitric acid are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 4
In the preparation catalyst step 2 of present embodiment, with the 2.0g mass fraction is that 4% aqueous solution of nitric acid joins in the 2.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 1, stir, dropping ammonia is regulated pH to 6～7, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 0.5, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine, moisture and nitric acid are taken off in 400 ℃ of roastings 12 hours, are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 5
In the preparation catalyst step 2 of present embodiment, with the 4.0g mass fraction is that 4% aqueous solution of nitric acid joins in the 12.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 3, stir, dropping ammonia is regulated pH to 6～7, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 3, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine, moisture and nitric acid are taken off in 400 ℃ of roastings 12 hours, are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 6
In the preparation catalyst step 2 of present embodiment, it is in 4% the aqueous solution of nitric acid that 0.7g two oxalic acid hydrates are dissolved in the 6.4g mass fraction, two oxalic acid hydrates and mass fraction are that the mass ratio of 4% aqueous solution of nitric acid is 1: 9, the gained mixed liquor joins in the 8.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 1.25, stir, dropping ammonia is regulated pH to 6～7, add 4.0gCoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 2, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine is taken off in 400 ℃ of roastings 12 hours, moisture and nitric acid are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 7
In the preparation catalyst step 2 of present embodiment, it is in 4% the aqueous solution of nitric acid that 0.4g two oxalic acid hydrates are dissolved in the 2.0g mass fraction, two oxalic acid hydrates and mass fraction are that the mass ratio of 4% aqueous solution of nitric acid is 1: 5, the gained mixed liquor joins in the 2.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 1, stir, dropping ammonia is regulated pH to neutral, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 0.5, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine is taken off in 400 ℃ of roastings 12 hours, moisture and nitric acid are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 8
In the preparation catalyst step 2 of present embodiment, it is in 4% the aqueous solution of nitric acid that 0.3g two oxalic acid hydrates are dissolved in the 4.0g mass fraction, two oxalic acid hydrates and mass fraction are that the mass ratio of 4% aqueous solution of nitric acid is 1: 13, the gained mixed liquor joins in the 12.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 3, stir, dropping ammonia is regulated pH to 6～7, add 4.0gCoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 3, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine is taken off in 400 ℃ of roastings 12 hours, moisture and nitric acid are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 9
In the preparation catalyst step 2 of present embodiment, it is in 4% the aqueous solution of nitric acid that 0.512g two oxalic acid hydrates and 0.256g sodium metasilicate are dissolved in the 6.4g mass fraction, sodium metasilicate and two oxalic acid hydrates, mass fraction is that the mass ratio of 4% aqueous solution of nitric acid is 1: 2: 25, the gained mixed liquor joins in the 8.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 1.25, stir, dropping ammonia is regulated pH to 6～7, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 2, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine is taken off in 400 ℃ of roastings 12 hours, moisture and nitric acid are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 10
In the preparation catalyst step 2 of present embodiment, it is in 4% the aqueous solution of nitric acid that 0.2g two oxalic acid hydrates and 0.2g sodium metasilicate are dissolved in the 2.0g mass fraction, sodium metasilicate and two oxalic acid hydrates, mass fraction is that the mass ratio of 4% aqueous solution of nitric acid is 1: 1: 10, the gained mixed liquor joins in the 2.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 1, stir, dropping ammonia is regulated pH to 6～7, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 0.5, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine is taken off in 400 ℃ of roastings 12 hours, moisture and nitric acid are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 11
In the preparation catalyst step 2 of present embodiment, it is in 4% the aqueous solution of nitric acid that 0.81g two oxalic acid hydrates and 0.27g sodium metasilicate are dissolved in the 4.0g mass fraction, sodium metasilicate and two oxalic acid hydrates, mass fraction is that the mass ratio of 4% aqueous solution of nitric acid is 1: 3: 15, the gained mixed liquor joins in the 12.0g nano-aluminum hydroxide, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of nano-aluminum hydroxide are 1: 3, stir, dropping ammonia is regulated pH to 6～7, add 4.0g CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and nano-aluminum hydroxide is 1: 3, stir, knead into the ball that particle diameter is 3～6mm, diethylenetriamine is taken off in 400 ℃ of roastings 12 hours, moisture and nitric acid are chilled to room temperature naturally.Other steps are identical with embodiment 1, are prepared into catalyst.
Embodiment 12
In the synthetic CoSAPO-101 molecular sieve step 1 of embodiment 1～11, be 85% phosphoric acid and ethyl orthosilicate, cobalt acetate, boehmite, diethylenetriamine, distilled water by the mol ratio of P element and Si element, Co element, Al element, diethylenetriamine, distilled water with mass fraction it is 1: 0.02: 0.25: mix at 0.3: 0.5: 40, regulating pH with acetic acid and ammoniacal liquor is 5.0, and other steps of this step are identical with embodiment 1.Other steps are identical with corresponding embodiment, are prepared into catalyst.
Embodiment 13
In the synthetic CoSAPO-101 molecular sieve step 1 of embodiment 1～11, be 85% phosphoric acid and ethyl orthosilicate, cobalt acetate, boehmite, diethylenetriamine, distilled water by the mol ratio of P element and Si element, Co element, Al element, diethylenetriamine, distilled water with mass fraction it is 1: 0.1: 0.6: mix at 0.9: 1.0: 100, regulating the pH value with acetic acid and ammoniacal liquor is 7.0, and other steps of this step are identical with embodiment 1.Other steps are identical with corresponding embodiment, are prepared into catalyst.
Embodiment 14
In the synthetic CoSAPO-101 molecular sieve step 1 of embodiment 1～13, raw materials used cobalt acetate is replaced with cobaltous sulfate, boehmite is replaced with nano-aluminum hydroxide, and the molal quantity of Co element and Al element is identical with corresponding embodiment, and other steps of this step are identical with corresponding embodiment.In preparation catalyst step 2, nano-aluminum hydroxide such as uses to replace at the aluminium oxide of quality, and other steps of this step are identical with corresponding embodiment, are prepared into catalyst.
Embodiment 15
In the synthetic CoSAPO-101 molecular sieve step 1 of embodiment 1～13, raw materials used cobalt acetate is replaced with cobalt chloride, and the molal quantity of Co element is identical with corresponding embodiment, and other steps of this step are identical with corresponding embodiment.In preparation catalyst step 2, nano-aluminum hydroxide such as uses to replace at the boehmite of quality, and other steps of this step are identical with corresponding embodiment, are prepared into catalyst.
Embodiment 16
In the preparation catalyst step 2 of embodiment 1～13, nano-aluminum hydroxide such as uses to replace at the silica of quality, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into catalyst.
Embodiment 17
In the preparation catalyst step 2 of embodiment 1～13, nano-aluminum hydroxide such as uses to replace at the magnesia of quality, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into catalyst.
Embodiment 18
In the synthetic CoSAPO-101 molecular sieve step 1 of embodiment 1～17, it is in the withstand voltage reactor of polytetrafluoroethylene (PTFE) that the mixture that mixes is regulated the liner of packing into behind the pH with acetic acid and ammoniacal liquor, reactor is put into baking oven, be warming up to 160 ℃, isothermal reaction 72 hours cools, filter, crystal was put into 60 ℃ of dryings of baking oven 10 hours with distilled water washing 2～5 times, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into catalyst.
Embodiment 19
In the synthetic CoSAPO-101 molecular sieve step 1 of embodiment 1～17, it is in the withstand voltage reactor of polytetrafluoroethylene (PTFE) that the mixture that mixes is regulated the liner of packing into behind the pH with acetic acid and ammoniacal liquor, put into baking oven, be warming up to 220 ℃, isothermal reaction 4 hours cools, filter, crystal was put into 100 ℃ of dryings of baking oven 5 hours with distilled water washing 2～5 times, and other steps of this step are identical with corresponding embodiment.Other steps are identical with corresponding embodiment, are prepared into catalyst.
In order to prove beneficial effect of the present invention, the inventor is used for preparing light olefins from methanol with the catalyst of preparation in the embodiment of the invention 1,2,3,6,9, and the activity of evaluate catalysts is specifically tested as follows:
1, laboratory apparatus
(1) the mobile microreactor of homemade fixed bed atmospheric pressure, as shown in Figure 1.In Fig. 1, the mobile microreactor of fixed bed atmospheric pressure is made of nitrogen steel cylinder 1, spinner flowmeter 2, constant flow pump 3, stock bottle 4, PID temperature controller 5, drier 6, gas-liquid separator 7, condenser pipe 8, temp controlled meter 9, armoured thermocouple 10, reactor 11 UNICOMs.
(2) gas chromatograph, model are GC5890C, are sold by the prompt analytical instrument Applied Research Laboratory of Nanjing section.
2, preparing light olefins from methanol catalytic reaction
0.8mL quartz sand is inserted reactor 11 as supporting bed, 2.7g catalyst is packed into reactor 11 as beds, on beds, dose 58mL quartz sand again, with the fixed catalyst bed, the coupled reaction device, the air-tightness of opening nitrogen cylinder 1 feeding nitrogen testing fixture utilizes the tube furnace by 5 controls of PID temperature controller that reactor 11 is heated to 200 ℃ to air tight, by regulating spinner flowmeter 2, control N
2Flow be 15mL/min, make catalyst under this state, activate 2 hours.Reactor 11 is warming up to 445 ℃, behind question response device 11 constant temperature, open constant flow pump 3, the material liquid that with the volume ratio of methyl alcohol and distilled water in the stock bottle 4 is 1: 3 is with in the sample introduction speed injecting reactor 11 of constant flow pump 3 with 0.25mL/min, carry out catalytic reaction, measure the temperature of beds in chemical reaction process with armoured thermocouple 10, the temperature in the reactor 11 is shown by temp controlled meter 9; Product enters condenser pipe 8 condensations, separates through gas-liquid separator 7, and liquid product is collected from gas-liquid separator 7 bottoms, gas-phase product by drier 6 backs with the online sampling of syringe after emptying, reacted 4 minutes, begin to gather gas phase, liquid phase sample carries out on-line analysis.Reaction result and product analysis in table 1.
Table 1 different catalysts is used for the catalytic reaction result of preparing light olefins from methanol
By table 1 as seen, the catalyst of the present invention preparation is used for preparing light olefins from methanol and has higher ethylene selectivity, reach about 60%, and the overall selectivity of ethene and propylene reaches about 80%, and conversion of methanol also can reach more than 81%.
Claims (7)
1. Preparation of catalysts method that is used for preparing light olefins from methanol is characterized in that being made up of following step:
(1) synthetic CoSAPO-101 molecular sieve
With mass fraction 85% phosphoric acid and ethyl orthosilicate, the cobalt source, the aluminium source, diethylenetriamine, distilled water is pressed P element and Si element, the Co element, the Al element, diethylenetriamine, the mol ratio of distilled water is 1: 0.02～0.1: 0.25～0.6: 0.3～0.9: 0.5～1.0: 40～100 to mix, regulating pH with acetic acid or ammoniacal liquor is 5.0～7.0, the liner of packing into is in the withstand voltage reactor of polytetrafluoroethylene (PTFE), reactor is put into baking oven, be warming up to 160～220 ℃, isothermal reaction 4～72 hours, cool, filter, crystal washs 2～5 times with distilled water, put into 60～100 ℃ of dryings of baking oven 5～10 hours, and be prepared into the CoSAPO-101 molecular sieve;
Above-mentioned cobalt source is cobalt acetate or cobaltous sulfate or cobalt chloride; The aluminium source is nano-aluminum hydroxide or boehmite;
(2) preparation catalyst
The CoSAPO-101 molecular sieve is put into ball mill grind to form fine powder below 400 orders, obtain CoSAPO-101 molecular sieve fine powder; With mass fraction is that 4% aqueous solution of nitric acid or two oxalic acid hydrates and mass fraction are that the mass ratio of 4% aqueous solution of nitric acid is 1: 5～13 mixed liquor or sodium metasilicate and two oxalic acid hydrates, mass fraction is that the mass ratio of 4% aqueous solution of nitric acid is that 1: 1～3: 10～25 mixed liquor joins in the binding agent, mass fraction is that 4% the aqueous solution of nitric acid and the mass ratio of binding agent are 1: 1～3, stir, dropping ammonia is regulated pH to 6～7, add CoSAPO-101 molecular sieve fine powder, the mass ratio of CoSAPO-101 molecular sieve fine powder and binding agent is 1: 0.5～3, stir, knead into the ball that particle diameter is 3～6mm, 350～480 ℃ of roastings 5～12 hours, naturally be chilled to room temperature, be prepared into catalyst;
Above-mentioned binding agent is any one in aluminium oxide, nano-aluminum hydroxide, boehmite, silica, the magnesia.
2. the Preparation of catalysts method that is used for preparing light olefins from methanol according to claim 1, it is characterized in that: in synthetic CoSAPO-101 molecular sieve step (1), mass fraction is that the mol ratio of P element and Si element in 85% phosphoric acid and ethyl orthosilicate, cobalt source, aluminium source, diethylenetriamine, the distilled water, Co element, Al element, diethylenetriamine, distilled water is 1: 0.06: 0.36: 0.57: 0.73: 67.
3. the Preparation of catalysts method that is used for preparing light olefins from methanol according to claim 1 is characterized in that: in synthetic CoSAPO-101 molecular sieve step (1), reaction temperature is 180 ℃, and the reaction time is 24 hours.
4. the Preparation of catalysts method that is used for preparing light olefins from methanol according to claim 1 is characterized in that: in preparation catalyst step (2), the mass ratio of CoSAPO-101 molecular sieve fine powder and binding agent is 1: 2.
5. the Preparation of catalysts method that is used for preparing light olefins from methanol according to claim 1 is characterized in that: in synthetic CoSAPO-101 molecular sieve step (1), described cobalt source is a cobalt acetate.
6. the Preparation of catalysts method that is used for preparing light olefins from methanol according to claim 1 is characterized in that: in synthetic CoSAPO-101 molecular sieve step (1), described aluminium source is a boehmite.
7. the Preparation of catalysts method that is used for preparing light olefins from methanol according to claim 1 is characterized in that: in preparation catalyst step (2), described binding agent is a nano-aluminum hydroxide.
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| CN110801862A (en) * | 2019-10-24 | 2020-02-18 | 杜成荣 | Catalyst for preparing low-carbon olefin from methanol |
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| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN101239729A (en) * | 2008-01-30 | 2008-08-13 | 陕西师范大学 | Method for preparing metallic silicon phosphorus aluminum molecular screen |
| CN101318667A (en) * | 2008-07-18 | 2008-12-10 | 上海兖矿能源科技研发有限公司 | Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN101239729A (en) * | 2008-01-30 | 2008-08-13 | 陕西师范大学 | Method for preparing metallic silicon phosphorus aluminum molecular screen |
| CN101318667A (en) * | 2008-07-18 | 2008-12-10 | 上海兖矿能源科技研发有限公司 | Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof |
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| 《化学学报》 19950630 白云山 等 在二乙烯三胺体系中含钴磷酸铝分子筛新相的合成 , 第6期 * |
| 《无机化学学报》 20100930 白云山 等 CoSAPO-101分子筛大单晶的合成与表征 第26卷, 第9期 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110801862A (en) * | 2019-10-24 | 2020-02-18 | 杜成荣 | Catalyst for preparing low-carbon olefin from methanol |
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