CN102029184A - Catalyst used in process of preparing dimethyl ether from methanol on fluidized bed and preparation method thereof - Google Patents
Catalyst used in process of preparing dimethyl ether from methanol on fluidized bed and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst used in the process of preparing dimethyl ether from methanol on a fluidized bed, which is prepared by a method comprising the following steps of: uniformly mixing desalted water and a silicon-containing material, adding an aluminum-containing material and silicon aluminum phosphorus molecular sieves, uniformly mixing, adding a base material, uniformly mixing to obtain slurry, adjusting a pH value to ensure that the slurry forms a gel state, continuously stirring, pelleting by spraying so as to obtain solid microspheres, roasting, acid-washing, drying and roasting to obtain the catalyst which has the abrasion index of 0.5 to 2.0 and is used in the process of preparing the dimethyl ether from the methanol on the fluidized bed. The hollow degree of the solid microspheres can be lowered by the catalyst prepared by the method, while the catalytic activity is met, the wear-resisting property of the catalyst is obviously improved, and the abrasion index of the catalyst is below 2.0 and can be below 1.5 by optimizing preparation parameters; and the catalyst has high stability and long service life and is characterized by low reaction temperature, high methanol conversion ratio, high selectivity of the dimethyl ether and low cost, and the large-scale production of the dimethyl ether can be realized by the catalyst.
Description
Technical field
The invention belongs to the Preparation of Catalyst field.The Catalysts and its preparation method that relates to a kind of preparing dimethyl ether from methanol.
Background technology
Dimethyl ether is a kind of colourless gas with ether flavor under normal pressure, as a kind of emerging basic chemical raw materials, because its good easy compression, condensation, vaporizing property makes dimethyl ether that the purposes of many uniquenesses be arranged in chemical industry such as pharmacy, fuel, agricultural chemicals.Can replace fluorine Lyons as aerosol propellant and refrigerant as highly purified dimethyl ether, reduce the pollution of atmospheric environment and the destruction of ozone layer.Because its good water-solubility, oil-soluble make its range of application be better than petrochemicals such as propane, butane greatly.Replace the new raw material of methyl alcohol, can obviously reduce the Formaldehyde Production cost, in large-scale formaldehyde plant, more demonstrate its superiority as Formaldehyde Production.As its accumulating of domestic fuel gas, combustion safety, performance indications such as premix gas calorific value and theoretical temperature combustion all are better than oil liquefied gas, can be used as peak regulation gas, the liquefied gas mixed gas of urban duct coal gas.Dimethyl ether also is the ideal fuels of Diesel engine, compares with methanol fuel automobile, does not have the cold-starting automobile problem.Its will still produce one of primary raw material of low-carbon alkene future simultaneously.
The production technology of dimethyl ether can be divided two kinds substantially: one-step method and two step method.One-step method is directly to generate dimethyl ether by unstripped gas (synthesis gas), and is immature on the technology at present; Two step method is an at first synthesizing methanol of synthesis gas, and then dimethyl ether preparation by dehydrating.The two step method dimethyl ether synthesis is the main technique that at present domestic and international dimethyl ether is produced, and is divided into two kinds of liquid phase methanol dehydration method and gas phase methanol dehydration methods.
Preparing dimethyl ether by dewatering methanol adopts sulfuric acid as catalyst the earliest, is reflected in the liquid phase and carries out, and therefore is called liquid phase methanol dehydration method, is also referred to as sulfuric acid process.The dimethyl ether product of this explained hereafter purity 99.6% is used for some occasions not high to the dimethyl ether purity requirement.Characteristics such as its technology has reaction condition gentleness (130～160 ℃), methyl alcohol conversion per pass height (＞85%), can intermittently also can produce continuously, but there are problems such as equipment corrosion, environmental pollution are serious, product post processing difficulty, abolished this method abroad substantially.Chinese patent ZL01107996.7 has announced and a kind of the improved method of liquid phase methanol dehydration method has been reduced the spent acid discharging that the maximum production capacity of separate unit reactor is 3.3 ten thousand tons/year at present.
The gas-phase methanol evaporation is that methanol steam makes dimethyl ether by the solid acid catalyst catalytic dehydration in fixed bed reactors.This process characteristic is simple to operate, and automaticity is higher, a small amount of waste water and gas discharging, and emission is lower than national specified discharge standard.This method is the main method of producing dimethyl ether at present both at home and abroad.Chinese patent ZL95113028.5 has announced a kind of method of gas-phase methanol preparing dimethy ether, adopts multistage chilling-type reactor, is catalyst with γ-A12O3.Because preparing dimethyl ether by dewatering methanol is exothermic reaction, there is the problem of heat-obtaining difficulty in fixed bed reactors, the amplification of restriction fixed bed reactors.Adopt γ-A1 simultaneously
2O
3Need higher reaction temperature, easily generate the hydro carbons byproduct, stable unfavorable to catalyst.
Compare with the fixed bed phase reactor, the characteristics that fluidized-bed reactor has easy heat-obtaining, amplifies easily, the inside reactor temperature is even.Chinese patent application CN101417228A discloses a kind of fluidization catalyst of producing dimethyl ether by dehydrating methanol.But patent application is not optimized at described various molecular sieves, because the acidity of different molecular sieve has very big difference, is used for the preparing dimethyl ether from methanol process, and the conversion ratio of reaction and selectivity have very big difference.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol is provided.
Second purpose of the present invention provides a kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol.
Technical scheme of the present invention is summarized as follows:
A kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol, make with following method:
Desalted water and siliceous mixing of materials is even, add aluminiferous material and sial phosphorus molecular sieve, mix, add matrix material, mix, obtain to contain admittedly slurries for 10wt%～60wt%, regulate between slurry pH value to 2.5～4.0, make described slurries be gel, continue to stir 1～24 hour, pass through mist projection granulating, obtain microspheres with solid, with the roasting of described microspheres with solid process, through concentration is the aqueous hydrochloric acid solution of 0.01mol/L～2mol/L, aqueous solution of nitric acid, aqueous sulfuric acid, at least a in aqueous acetic acid and the aqueous ammonium chloride solution carries out pickling after 0.1～10 hour, drying, roasting, the acquisition abrasion index is 0.5～2.0 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, and described matrix material is a kaolin, clay, imvite, at least a in bentonite and the bentonite.
Preferably; Slurry pH value is 3.1～3.8.
The described silicon materials that contains is at least a in Ludox, sodium metasilicate and the silicic acid.
Described aluminiferous material is at least a in aluminium colloidal sol, boehmite, active alundum (Al, aluminium chlorohydrate and the hydration alundum (Al.
Described sial phosphorus molecular sieve is one or more in SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56 or the above-mentioned molecular sieve crossed with alkali metals modified.
Described sial phosphorus molecular sieve, the mass ratio that contains silica, the alundum (Al in the aluminiferous material and matrix material in the silicon materials are (5～40): (1～25): (1～25): (20～65).
Described sial phosphorus molecular sieve, the mass ratio that contains silica, the alundum (Al in the aluminiferous material and matrix material in the silicon materials are (10～25): (10～15): (15～20): (40～60).
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and siliceous mixing of materials is even, add aluminiferous material and sial phosphorus molecular sieve, mix, add matrix material, mix, obtain to contain admittedly slurries for 10wt%～60wt%, regulate between slurry pH value to 2.5～4.0, make described slurries be gel, continue to stir 1～24 hour, pass through mist projection granulating, obtain microspheres with solid, with the roasting of described microspheres with solid process, through concentration is the aqueous hydrochloric acid solution of 0.01mol/L～2mol/L, aqueous solution of nitric acid, aqueous sulfuric acid, at least a in aqueous acetic acid and the aqueous ammonium chloride solution carries out pickling after 0.1～10 hour, drying, roasting, the acquisition abrasion index is 0.5～2.0 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, and described matrix material is a kaolin, clay, imvite, at least a in bentonite and the bentonite.
Described slurry pH value is 3.1～3.8.
The described silicon materials that contains is at least a in Ludox, sodium metasilicate and the silicic acid.
Described aluminiferous material is at least a in aluminium colloidal sol, boehmite, active alundum (Al, aluminium chlorohydrate and the hydration alundum (Al.
Described sial phosphorus molecular sieve is one or more in SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56 or the above-mentioned molecular sieve crossed with alkali metals modified.
Described sial phosphorus molecular sieve, the mass ratio that contains silica, the alundum (Al in the aluminiferous material and matrix material in the silicon materials are (5～40): (1～25): (1～25): (20～65).
Described sial phosphorus molecular sieve, the mass ratio that contains silica, the alundum (Al in the aluminiferous material and matrix material in the silicon materials are (10～25): (10～15): (15～20): (40～60).
The technical program has following characteristics:
1. under gel state, carry out mist projection granulating,, make material be gel state, under gel state, carry out mist projection granulating by regulating the pH value of slurries.Because gel is mobile relatively poor, therefore need careful pH value of regulating slurries.In pH scope of the present invention, gel had both had good flowing, and can obtain solid microspheres with solid by granulation formation again;
2. method of the present invention can obviously be improved the flowability of slurries, reduces the hollow degree of microspheres with solid, when satisfying the catalyst activity, significantly improves the anti-wear performance of catalyst of the present invention.
3. catalyst abrasion index of the present invention is lower than 2.0, and by optimizing preparation parameter, abrasion index can be lower than 1.5.
This clearly demarcated a kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol can satisfy the requirement of the technological process that is used for the fluid bed preparing dimethyl ether from methanol fully, has good stability, the life-span is long, abrasion index is low characteristics.Utilize catalyst of the present invention can carry out dimethyl ether large-scale production, have that reaction temperature is low, methanol conversion is high, a dimethyl ether selectivity height, characteristics that cost is low.
The specific embodiment
The abrasion index of fluid catalyst adopts the method for air-spray to measure according to standard A STM D5757-95.Concrete grammar is a certain amount of catalyst of packing in the abrasion index determinator, after the air wetting with certain flow, the attrition tube that three apertures are arranged by a bottom at a high speed, catalyst is carried out repeatedly purging, and the catalyst fines that wearing and tearing come off is collected by specific powder filter gathering-device.Continue after 1 hour, weighing blows out the weight of fine powder; The powder filter gathering-device that more renews continues to purge 3 hours under original condition, and weighing blows out the weight of fine powder and stays the interior catalyst weight of attrition tube, calculates the abrasion index of sample according to formula.
In the preparing dimethyl ether from methanol technical process, the methyl alcohol catalytic dehydration generates the dimethyl ether reaction in fluidized-bed reactor, and after product was separated through piece-rate system, dimethyl ether was stored as product, unreacted methanol is returned fluidized-bed reactor and is continued reaction, effluxes after the processing of waste water process is up to standard; Piece-rate system comprises that the fixed gas that is used for removing the product fixed gas removes tower and is used for the dimethyl ether rectifying column of separation of dimethyl ether, first alcohol and water.
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and Ludox are mixed, add boehmite and SAPO-18, mix, add kaolin, mixing, obtain to contain admittedly slurries for 40wt%, stir, regulating the pH value is 3.1, make described slurries be gel, continue to stir 1 hour, pass through mist projection granulating, obtain microspheres with solid, again after 600 ℃ of roastings, be the aqueous ammonium chloride solution pickling of 0.5mol/L after 4 hours through concentration, again after drying and the 550 ℃ of roastings, the acquisition abrasion index is 1.4 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described SAPO-18, silica in the Ludox, alundum (Al in the boehmite and kaolinic mass ratio are 15: 10: 15: 60.
The above-mentioned finished catalyst of 200g is packed in the fixed fluidized-bed reactor of diameter 100mm, carry out methyl alcohol catalytic dehydration reaction of preparing dimethyl ether.Reaction temperature is 245 ℃, and the methanol feeding weight space velocity is 3.75h
-1, methanol conversion is 82.5%, the dimethyl ether selectivity is 100%.
Embodiment 2
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and Ludox are mixed, add boehmite and SAPO-34, mix, add imvite, mixing obtains to contain admittedly the slurries for 45wt%, stirs, regulating the pH value is 3.8, make described slurries be gel, continue to stir 1 hour, pass through mist projection granulating, obtain microspheres with solid, again after 600 ℃ of roastings, through the aqueous solution of nitric acid pickling of 0.5mol/L after 2 hours, again after drying and the 550 ℃ of roastings, the acquisition abrasion index is 1.5 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described SAPO-34, silica in the Ludox, alundum (Al in the boehmite and kaolinic mass ratio are 25: 10: 20: 45.
The above-mentioned finished catalyst of 200g is packed in the fixed fluidized-bed reactor of diameter 100mm, carry out methyl alcohol catalytic dehydration reaction of preparing dimethyl ether.Reaction temperature is 240 ℃, and the methanol feeding weight space velocity is 3.75h
-1, methanol conversion is 80.3%, the dimethyl ether selectivity is 100%.
Embodiment 3
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and Ludox are mixed, add boehmite and SAPO-34, mix, add kaolin, mixing obtains to contain admittedly the slurries for 40wt%, stirs, regulating the pH value is 3.1, make described slurries be gel, continue to stir 1 hour, pass through mist projection granulating, obtain microspheres with solid, again after 600 ℃ of roastings, through the aqueous acetic acid pickling of 1.0mol/L after 10 hours, again after drying and the 550 ℃ of roastings, the acquisition abrasion index is 1.3 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described SAPO-34, silica in the Ludox, alundum (Al in the boehmite and kaolinic mass ratio are 15: 20: 5: 60.
The above-mentioned finished catalyst of 200g is packed in the fixed fluidized-bed reactor of diameter 100mm, carry out methyl alcohol catalytic dehydration reaction of preparing dimethyl ether.Reaction temperature is 230 ℃, and the methanol feeding weight space velocity is 3.75h
-1, methanol conversion is 82.7%, the dimethyl ether selectivity is 100%.
Embodiment 4
A kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol is to make with following method:
Desalted water and sodium metasilicate are mixed, add active alundum (Al and SAPO-11, mix, add clay, mixing obtains to contain admittedly the slurries for 40wt%, stirs, regulating the pH value is 4.0, make described slurries be gel, continue to stir 1 hour, pass through mist projection granulating, obtain microspheres with solid, again after 600 ℃ of roastings, through the aqueous sulfuric acid pickling of 0.25mol/L after 10 hours, drying and 550 ℃ of roastings again, the acquisition abrasion index is 1.9 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described SAPO-11, silica in the sodium metasilicate, the alundum (Al in the active alundum (Al and the mass ratio of clay are 20: 25: 5: 50.
The above-mentioned finished catalyst of 200g is packed in the fixed fluidized-bed reactor of diameter 100mm, carry out methyl alcohol catalytic dehydration reaction of preparing dimethyl ether.Reaction temperature is 250 ℃, and the methanol feeding weight space velocity is 3.75h
-1, methanol conversion is 79.4%, the dimethyl ether selectivity is 100%.
Embodiment 5
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and silicic acid are mixed, add aluminium colloidal sol and SAPO-18 and SAPO-34, mix, add kaolin, mixing, obtain to contain admittedly slurries for 40wt%, stir, regulating the pH value is 4.0, make described slurries be gel, continue to stir 1 hour, pass through mist projection granulating, obtain microspheres with solid, again after 600 ℃ of roastings, through the aqueous solution of nitric acid pickling of 0.5mol/L after 4 hours, drying and 550 ℃ of roastings again, the acquisition abrasion index is 0.9 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described SAPO-18, SAPO-34, silica in the silicic acid, alundum (Al in the aluminium colloidal sol and kaolinic mass ratio are 10: 10: 20: 10: 50.
The above-mentioned finished catalyst of 200g is packed in the fixed fluidized-bed reactor of diameter 100mm, carry out methyl alcohol catalytic dehydration reaction of preparing dimethyl ether.Reaction temperature is 250 ℃, and the methanol feeding weight space velocity is 3.75h
-1, methanol conversion is 79.4%, the dimethyl ether selectivity is 100%.
Embodiment 6
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and Ludox are mixed, add boehmite and SAPO-5, SAPO-34, mix, add kaolin, mixing, obtain to contain admittedly slurries for 40wt%, stir, regulating the pH value is 2.5, make described slurries be gel, continue to stir 1 hour, pass through mist projection granulating, obtain microspheres with solid, again after 600 ℃ of roastings, through the aqueous ammonium chloride solution pickling of 0.5mol/L after 4 hours, drying and 550 ℃ of roastings again, the acquisition abrasion index is 1.2 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described SAPO-5, SAPO-34, silica in the Ludox, alundum (Al in the boehmite and kaolinic mass ratio are 7: 8: 15: 15: 55.
The above-mentioned finished catalyst of 200g is packed in the fixed fluidized-bed reactor of diameter 100mm, carry out methyl alcohol catalytic dehydration reaction of preparing dimethyl ether.Reaction temperature is 230 ℃, and the methanol feeding weight space velocity is 3.75h
-1, methanol conversion is 81.3%, the dimethyl ether selectivity is 100%.
Embodiment 7
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and Ludox are mixed, add boehmite and SAPO-34, mix, add kaolin, mixing obtains to contain admittedly the slurries for 40wt%, stirs, regulating the pH value is 3.5, make described slurries be gel, continue to stir 1 hour, pass through mist projection granulating, obtain microspheres with solid, again through 600 ℃ of roastings, through the aqueous ammonium chloride solution pickling of 0.5mol/L 4 hours, drying and 550 ℃ of roastings again, the acquisition abrasion index is 1.1 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described SAPO-34, silica in the Ludox, alundum (Al in the boehmite and kaolinic mass ratio are 15: 15: 15: 55.
The 5kg finished catalyst is put into the hot small testing device of recirculating fluidized bed to react, the reactor catalyst reserve is 1.5kg, and the catalyst circulation amount is 0.5-1.5kg/hr, and reaction temperature is 220～230 ℃, raw material is 80% methanol aqueous solution, and the methanol feeding weight space velocity is 3.0h
-1, methanol conversion is 85.2%, the dimethyl ether selectivity is 100%.
Embodiment 8
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and sodium metasilicate are mixed, add aluminium chlorohydrate and SAPO-8, mix, add imvite, mixing, obtain to contain admittedly the slurries for 10wt%, stir, regulating the pH value is 3.0, make described slurries be gel, continue to stir 12 hours,, obtain microspheres with solid by mist projection granulating, again through 580 ℃ of roastings, aqueous ammonium chloride solution pickling 4h through 0.5mol/L, again after drying and the 550 ℃ of roastings, obtain abrasion index and be 1.5 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, SAPO-8, silica in the sodium metasilicate, the alundum (Al in the aluminium chlorohydrate and the mass ratio of matrix material are 5: 1: 1: 93.
The 5kg finished catalyst is put into the hot small testing device of recirculating fluidized bed to react, the reactor catalyst reserve is 1.5kg, and the catalyst circulation amount is 0.5-1.5kg/hr, and reaction temperature is 220～230 ℃, raw material is 80% methanol aqueous solution, and the methanol feeding weight space velocity is 3.0h
-1, methanol conversion is 85.2%, the dimethyl ether selectivity is 100%.
Embodiment 9
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and sodium metasilicate are mixed, add hydration alundum (Al and SAPO-16, mix, add bentonite and bentonite, mixing, obtain to contain admittedly slurries for 60wt%, stir, regulating the pH value is 6.0, make described slurries be gel, continue to stir 10 hours,, obtain microspheres with solid by mist projection granulating, again through 620 ℃ of roastings, aqueous hydrochloric acid solution pickling 0.1h through 0.5mol/L, again after drying and the 550 ℃ of roastings, obtain abrasion index and be 2.0 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, SAPO-16, silica in the sodium metasilicate, alundum (Al in the hydration alundum (Al, the mass ratio of bentonite and bentonite is 40: 15: 20: 12: 13.
The 5kg finished catalyst is put into the hot small testing device of recirculating fluidized bed to react, the reactor catalyst reserve is 1.5kg, and the catalyst circulation amount is 0.5-1.5kg/hr, and reaction temperature is 220～230 ℃, raw material is 80% methanol aqueous solution, and the methanol feeding weight space velocity is 3.0h
-1, methanol conversion is 85.2%, the dimethyl ether selectivity is 100%.
Embodiment 10
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
With desalted water, sodium metasilicate and silicic acid mix, add hydration alundum (Al and SAPO-56, mix, add bentonite and bentonite (the two mass ratio is 1: 1), mixing, obtain to contain admittedly slurries for 50wt%, stir, regulating the pH value is 4.0, make described slurries be gel, continue to stir 24 hours,, obtain microspheres with solid by mist projection granulating, again through 650 ℃ of roastings, aqueous sulfuric acid pickling 5h through 0.5mol/L, again after drying and the 550 ℃ of roastings, obtain abrasion index and be 0.5 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described sial phosphorus molecular sieve, silica in sodium metasilicate and the silicic acid, the alundum (Al in the hydration alchlor and the mass ratio of matrix material are 25: 10: 5: 20: 40.
The 5kg finished catalyst is put into the hot small testing device of recirculating fluidized bed to react, the reactor catalyst reserve is 1.5kg, and the catalyst circulation amount is 0.5-1.5kg/hr, and reaction temperature is 220～230 ℃, raw material is 80% methanol aqueous solution, and the methanol feeding weight space velocity is 3.0h
-1, methanol conversion is 85.2%, the dimethyl ether selectivity is 100%.
Embodiment 11
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and sodium metasilicate are mixed, add aluminium chlorohydrate, hydration alundum (Al and SAPO-17, mix, add bentonite, mixing, obtain to contain admittedly slurries for 50wt%, stir, regulating the pH value is 4.0, make described slurries be gel, continue to stir 24 hours,, obtain microspheres with solid by mist projection granulating, again through 650 ℃ of roastings, aqueous ammonium chloride solution pickling 6h through 0.5mol/L, again after drying and the 550 ℃ of roastings, obtain abrasion index and be 0.5 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described sial phosphorus molecular sieve, silica in the sodium metasilicate, the alundum (Al in aluminium chlorohydrate and the hydration alundum (Al and the mass ratio of matrix material are 40: 25: 25: 10.
The 5kg finished catalyst is put into the hot small testing device of recirculating fluidized bed to react, the reactor catalyst reserve is 1.5kg, and the catalyst circulation amount is 0.5-1.5kg/hr, and reaction temperature is 220～230 ℃, raw material is 80% methanol aqueous solution, and the methanol feeding weight space velocity is 3.0h
-1, methanol conversion is 85.2%, the dimethyl ether selectivity is 100%.
Embodiment 12
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol comprises the steps:
Desalted water and sodium metasilicate are mixed, add hydration alundum (Al and SAPO-20, mix, add bentonite, mixing, obtain to contain admittedly the slurries for 50wt%, stir, regulating the pH value is 4.0, make described slurries be gel, continue to stir 24 hours,, obtain microspheres with solid by mist projection granulating, again through 650 ℃ of roastings, aqueous acetic acid pickling 5h through 0.5mol/L, again after drying and the 550 ℃ of roastings, obtain abrasion index and be 0.5 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, described sial phosphorus molecular sieve, contain the silica in the silicon materials, the alundum (Al in the aluminiferous material and the mass ratio of matrix material are 10: 15: 20: 55.
The 5kg finished catalyst is put into the hot small testing device of recirculating fluidized bed to react, the reactor catalyst reserve is 1.5kg, and the catalyst circulation amount is 0.5-1.5kg/hr, and reaction temperature is 220～230 ℃, raw material is 80% methanol aqueous solution, and the methanol feeding weight space velocity is 3.0h
-1, methanol conversion is 85.2%, the dimethyl ether selectivity is 100%.
SAPO-20 in one or more alternative present embodiments in the above-mentioned molecular sieve that can also cross with SAPO-31, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47 or with alkali metals modified also can prepare the catalyst that is used for the fluid bed preparing dimethyl ether from methanol.
Embodiment 13
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol is with embodiment 7:
Be reflected on 30,000 tons of methyl alcohol/year commerical test device and carry out, the reactor catalyst reserve is about 3700kg, and the catalyst circulation amount is 2600～2900kg/hr, and reaction temperature is 220～230 ℃, and material is 80% methanol aqueous solution, and the methanol feeding weight space velocity is 1.5
-1, reaction pressure is 0.2MPa, and methanol conversion is 92%, and the dimethyl ether selectivity is 99.2%.
Embodiment 14
A kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol is with embodiment 6:
The 5kg finished catalyst is put into the hot small testing device of recirculating fluidized bed to react, the reactor catalyst reserve is 1.5kg, and the catalyst circulation amount is 0.5-1.5kg/hr, and reaction temperature is 220～230 ℃, raw material is 80% methanol aqueous solution, and the methanol feeding weight space velocity is 3.0h
-1, methanol conversion is 85.2%, the dimethyl ether selectivity is 100%.
Claims (14)
1. catalyst that is used for the fluid bed preparing dimethyl ether from methanol is characterized in that making with following method:
Desalted water and siliceous mixing of materials is even, add aluminiferous material and sial phosphorus molecular sieve, mix, add matrix material, mix, obtain to contain admittedly slurries for 10wt%～60wt%, regulate between slurry pH value to 2.5～4.0, make described slurries be gel, continue to stir 1～24 hour, pass through mist projection granulating, obtain microspheres with solid, with the roasting of described microspheres with solid process, through concentration is the aqueous hydrochloric acid solution of 0.01mol/L-2mol/L, aqueous solution of nitric acid, aqueous sulfuric acid, at least a in aqueous acetic acid and the aqueous ammonium chloride solution carries out pickling after 0.1～10 hour, drying, roasting, the acquisition abrasion index is 0.5～2.0 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, and described matrix material is a kaolin, clay, imvite, at least a in bentonite and the bentonite.
2. a kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol according to claim 1 is characterized in that described slurry pH value is 3.1～3.8.
3. a kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol according to claim 1 is characterized in that the described silicon materials that contains is at least a in Ludox, sodium metasilicate and the silicic acid.
4. a kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol according to claim 1 is characterized in that described aluminiferous material is at least a in aluminium colloidal sol, boehmite, active alundum (Al, aluminium chlorohydrate and the hydration alundum (Al.
5. a kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol according to claim 1 is characterized in that described sial phosphorus molecular sieve is one or more in SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56 or the above-mentioned molecular sieve crossed with alkali metals modified.
6. a kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol according to claim 1, the mass ratio that it is characterized in that described sial phosphorus molecular sieve, contains silica, the alundum (Al in the aluminiferous material and matrix material in the silicon materials is (5～40): (1～25): (1～25): (20～65).
7. a kind of catalyst that is used for the fluid bed preparing dimethyl ether from methanol according to claim 6, the mass ratio that it is characterized in that described sial phosphorus molecular sieve, contains silica, the alundum (Al in the aluminiferous material and matrix material in the silicon materials is (10～25): (10～15): (15～20): (40～60).
8. a Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol is characterized in that comprising the steps:
Desalted water and siliceous mixing of materials is even, add aluminiferous material and sial phosphorus molecular sieve, mix, add matrix material, mix, obtain to contain admittedly slurries for 10wt%～60wt%, regulate between slurry pH value to 2.5～4.0, make described slurries be gel, continue to stir 1～24 hour, pass through mist projection granulating, obtain microspheres with solid, with the roasting of described microspheres with solid process, through concentration is the aqueous hydrochloric acid solution of 0.01mol/L～2mol/L, aqueous solution of nitric acid, aqueous sulfuric acid, at least a in aqueous acetic acid and the aqueous ammonium chloride solution carries out pickling after 0.1～10 hour, drying, roasting, the acquisition abrasion index is 0.5～2.0 the catalyst that is used for the fluid bed preparing dimethyl ether from methanol, and described matrix material is a kaolin, clay, imvite, at least a in bentonite and the bentonite.
9. a kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol according to claim 8 is characterized in that described slurry pH value is 3.1～3.8.
10. a kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol according to claim 8 is characterized in that the described silicon materials that contains is at least a in Ludox, sodium metasilicate and the silicic acid.
11. a kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol according to claim 8 is characterized in that described aluminiferous material is at least a in aluminium colloidal sol, boehmite, active alundum (Al, aluminium chlorohydrate and the hydration alundum (Al.
12. a kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol according to claim 8 is characterized in that described sial phosphorus molecular sieve is one or more in SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56 or the above-mentioned molecular sieve crossed with alkali metals modified.
13. a kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol according to claim 8, the mass ratio that it is characterized in that described sial phosphorus molecular sieve, contains silica, the alundum (Al in the aluminiferous material and matrix material in the silicon materials is (5～40): (1～25): (1～25): (20～65).
14. a kind of Preparation of catalysts method that is used for the fluid bed preparing dimethyl ether from methanol according to claim 13, the mass ratio that it is characterized in that described sial phosphorus molecular sieve, contains silica, the alundum (Al in the aluminiferous material and matrix material in the silicon materials is (10～25): (10～15): (15～20): (40～60).
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| CN102335623A (en) * | 2011-07-08 | 2012-02-01 | 中国天辰工程有限公司 | Fluidized bed catalyst and preparation method thereof |
| CN102553640A (en) * | 2011-12-31 | 2012-07-11 | 中国天辰工程有限公司 | Gel granulation method |
| CN116371463A (en) * | 2023-03-13 | 2023-07-04 | 中触媒新材料股份有限公司 | Low-attrition rate SAPO-34 molecular sieve catalyst, and preparation method and application thereof |
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| CN102553640A (en) * | 2011-12-31 | 2012-07-11 | 中国天辰工程有限公司 | Gel granulation method |
| CN102553640B (en) * | 2011-12-31 | 2013-06-05 | 中国天辰工程有限公司 | Gel granulation method |
| CN116371463A (en) * | 2023-03-13 | 2023-07-04 | 中触媒新材料股份有限公司 | Low-attrition rate SAPO-34 molecular sieve catalyst, and preparation method and application thereof |
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