CN1919451A - Catalyst for preparing dimethyl ether by methanol dehydration and its preparation method - Google Patents
Catalyst for preparing dimethyl ether by methanol dehydration and its preparation method Download PDFInfo
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Abstract
The invention discloses a dimethyl ether catalyst and preparing method through hydrating hydration tolerance and carbon deposit resistance carbinol, which is characterized by the following: adding rare earth element La and Ce in the catalyst to improve catalyst hydration tolerance stable property, adding Ca, Mg, Na and K to improve carbon deposit resistance of catalyst.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, particularly a kind of preparation method of dimethyl ether by methanol dewater.
Background technology
Dimethyl ether is broad-spectrum a kind of ether in the chemical industry, has characteristics such as nontoxic, safety, calorific value height, and can be used as propellant, diesel fuel, domestic fuel also is the intermediate of coal preparing liquid fuel simultaneously.It also is important basic chemical industry intermediate simultaneously, the relevant purposes widely at aspects such as pharmacy, agricultural chemicals, dyestuff, daily-use chemical industries.The method of producing dimethyl ether is as dehydration catalyst, because this method has bigger environmental pollution and to the seriously corroded of equipment the earliest with the concentrated sulfuric acid.Traditional production method be with methanol steam under 350～400 ℃, the pressure of 1.5MPa, make catalyst with aluminum phosphate and make.Improve it nearly decades, substituted the concentrated sulfuric acid with solid acid, is representative with alundum (Al, modification alundum (Al, molecular sieve, aluminum phosphate wherein.As the open 1984-16845 γ-Al of Japan Patent
2O
3As catalyst; The open 1984-42333 patent of Japan Patent with silicon-aluminium as dehydration catalyst; U.S. US4595785 is the γ-Al with the aluminium titanates modification
2O
3Making catalyst can improve reaction speed and prevent to tie charcoal; Japan Patent JP2-85224 is the γ-Al that has added a certain amount of IIIA family's metal and IVB modification
2O
3Do dehydration catalyst, its catalyst life can prolong; Chinese patent CN1164509A report prepares highly active catalyst with making catalyst with Ti, Zr modified ZSM-5, ZSM-11 and β-molecular sieve; CN1613558A report sulfate radical modification γ-Al
2O
3Be used as methanol dehydration catalyst; CN1151110C, CN1039392C, CN1106219C report adds lanthanum and titanium as modifier with infusion process.
Theoretically, for methyl alcohol condensation dehydration, strong more its activity of the acidity of catalyst is just strong more, but acidity is forced very much to such an extent that catalyst is very easily tied charcoal, and rapid inactivation.Too strong acidity also easily produces a large amount of accessory substances simultaneously, reduces its usefulness.If acidity too a little less than, just can cause reaction temperature, hypertonia, reactivity is crossed low or is not had activity fully, could guarantee that catalyst has high activity and selectivity so will allocate suitable acidity of catalyst.For the methanol dehydration system, the content of water is higher from another point of view, and catalyst reacts in the moisture system of height for a long time, traditional γ-Al
2O
3System Catalyst takes place because of hydration reaction, makes the crystal phase structure of catalyst change, and reduces the intensity and the activity of catalyst.The present invention is by suitable catalyst preparation process and add means such as auxiliary agent, develop water-fastly close, anti-carbon producing dimethyl ether by dehydrating methanol catalyst, when improving catalyst activity, raising catalyst water-fast closed, the anti-carbon performance.
Summary of the invention
Methyl alcohol condensation dehydration dimethyl ether-preparing course of reaction is: two methanol molecules are sloughed a part water in the presence of acidic catalyst, and two molecule methyl alcohol are condensed into a part dimethyl ether.Its reaction equation is as follows:
The object of the invention provides a kind of being easy to and makes, economical and practical producing dimethyl ether by dehydrating methanol catalyst and manufacture method thereof, catalyst performance stabilised, active high, the life-span is long, selectivity is high, raw materials for production economy is easy to get.This catalyst is characterised in that by adding the water-fast stability that closes that rare-earth elements La, Ce improve catalyst in the catalyst and in the technical process, improves the anti-carbon performance of catalyst by adding alkali metal such as proper C a, Mg, Na, K and alkaline-earth metal.
The present invention is that following process realizes:
At first be to produce the aluminum salt solution with certain feature, a kind of aluminium source is alchlor, aluminum sulfate or aluminum nitrate solution; Another kind of aluminium source is a sodium aluminate solution.Preparation contains La, Ce, Ca, Mg, Na, K are the salting liquid of auxiliary agent, preferably contains the salpeter solution of La, Ce, Ca, Mg, Na, K or in the hydrochloric acid solution one or more.Each composition weight percentage composition is: La:0.1～5%; Ce:0.1～5%; Ca:0.1～3%; Mg:0.1～3%; Na:0.01～1%; K:0.01～1%.The preferred weight percentage composition is: La:0.5～2%; Ce:0.5～2%; Ca:0.1～1%; Mg:0.1～1%; Na:0.1～0.6%; K:0.01～0.5%.
Method for preparing catalyst of the present invention is divided into two kinds of routes according to different aluminium sources:
The preparation of dry glue powder I:
A. preparation contains the aluminum salt solution of aluminium 1～6%wt, and preferred alchlor, aluminum sulfate or aluminum nitrate solution are made solution A; Slowly add above metering contain La, Ce, Ca, Mg are the solution of auxiliary agent, preferably contain the nitrate solution of La, Ce, Ca, Mg or in the hydrochloride solution one or more, make mixed solution B; Waterglass or Ludox that preparation contains silica 3～20%wt are solution C; 5～12% ammonia spirits are solution D.
Wherein, mixed material ratio in accordance with regulations mixes in stainless steel or enamel reaction mixing apparatus, and incorporation time generally must not fully mix it less than 1 hour.
B. in reactor, add water of certain end, stir, preferred mixing speed 80～300r/min, temperature preferably is controlled in 40～80 ℃ of scopes;
C. under the condition of pH value 7.3～8.5, solution A, solution B and solution D are carried out earlier and stream is neutralized into glue, and the time was generally 30～60 minutes, and temperature is to neutralize in 40～80 ℃ of scopes, add solution C, pH value 7～10, aging 1～3 hour;
D. more after filtration, the deionized water washing is some all over acid ion SO to stem-based catalyst
4 =, Cl
-, NO
3 -Less than 1.0%wt;
E. last washing is used and is contained the Na of above metering, the solution washing of K, preferred sodium nitrate, sodium carbonate or sodium hydroxide solution, and Na, K concentration are generally 0.01%～0.5%wt.Filter cake is through 110～140 ℃ of oven dry, and preferred drying time is 12～24 hours, has made catalyst dry glue powder I through pulverizing.
The preparation of dry glue powder II:
A. preparation earlier contains the sodium aluminate solution E of aluminium 1～6%wt, and above metering contain La, Ce, Ca, Mg are the solution of auxiliary agent, preferably contain the nitrate solution of La, Ce, Ca, Mg or in the hydrochloride solution one or more and make mixed solution B; Waterglass or Ludox that preparation contains silica 3～20%wt are solution C; 5～20% salpeter solutions or sulfuric acid solution are solution F; Carbon dioxide is neutralization medium G.
B. in reactor, add water of certain end, stir, preferred mixing speed 80～300r/min, temperature is controlled in 20～80 ℃ of scopes;
C. under the condition of pH value 7～9, solution E, solution C, solution B and solution F carry out and stream is neutralized into glue, and the time is 50～100 minutes, aging 1～3 hour; Also can replace solution F with neutralization medium G;
D. more after filtration, deionized water washing some all over Na ion to stem-based catalyst less than 1.0%wt.
E. filter cake was preferably dried 12～24 hours through 110～140 ℃ of oven dry, had made catalyst dry glue powder II through pulverizing.
The moulding of methanol dehydration catalyst is to take by weighing a certain amount of dry glue powder I or II, takes by weighing the extrusion aid of 0.5～2.0%wt again, and preferred: methylcellulose, sesbania gum etc., the two fully mixes.Mixed siccative adds binding agent again, mediates behind rare nitric acid of preferred 1%～6%wt, spirit of vinegar, aluminium colloidal sol, the Ludox, and the kneading time is not less than 0.5 hour, moulding then, can directly put into drying box after the moulding, can stir once in per 4 hours, and keep the discharge of moisture.Be preferably 12～24 hours drying time, calcined 1～10 hour down for preferred 450～600 ℃ at 300～800 ℃ dry back, and preferred 3～8 hours, the heating rate of calcining was generally 20 ℃～50 ℃/h, obtained finished catalyst.
Catalyst can be processed into catalyst Common Shape such as strip, clover shape, bunge bedstraw herb shape, ball-type, during for bar shaped, and the stripe shape of preferred φ 1～4mm.
Catalyst specific surface is 150～380m
2/ g is preferably 180～240m
2/ g, pore volume are 0.3～1.0ml/g, preferred 0.4～0.7ml/g, and the acid amount is controlled at 0.1～1.5mmol/g.
Finished catalyst each component percentage by weight consists of:
Al
2O
3：35～95％；SiO
2：1～50％；La：0.1～5％；Ce：0.1～5％；Ca：0.1～3％；Mg：0.1～3％；Na：：0.01～1％；K：0.01～1％。
Each component optimum weight percentage consists of:
Al
2O
3：80～90％；SiO
2：5～15％；La：0.5～2％；Ce：0.5～2％；Ca：0.1～1％；Mg：0.1～1％；Na：0.1～0.6％；K：0.01～0.5％。
Application of Catalyst is carried out in fixed bed, is specially adapted to uniform-temperature reactor, and catalyst places the reactor flat-temperature zone, does supporter with stainless (steel) wire and quartz sand up and down.The Application of Catalyst condition is pressure 0.2～6.0MPa, preferred 0.6～2.0MPa, most preferably 0.6～1.2MPa; Temperature is 180～450 ℃, preferred 180～350 ℃, and more preferably 200～300 ℃; Volume space velocity is 0.5～5.0h
-1, preferred 1.0～2.0h
-1
The analysis test method that the present invention is used:
1. the specific area of catalyst, pore volume and pore-size distribution are measured: adopt low-temperature nitrogen adsorption method, specific area is the BET specific area.
2. adopt the thing phase of X-ray diffractometer analysis of catalyst.
3. inductively coupled plasma spectral emissions instrument analysis of catalyst component.
4. the gas chromatographic analysis product is formed.
The present invention compared with prior art, the catalyst activity temperature is low, the operating procedure of Catalyst Production is simple, is suitable for industrial processes.
The specific embodiment
Embodiment 1
Get the aluminum trichloride solution 1000g that contains aluminium 3%wt, be solution A, lanthanum nitrate, each 20g of cerous nitrate solution with containing La, Ce5%wt contain Ca, Mg3%wt calcium nitrate, magnesium nitrate solution 10g, stir and suitable the heating down, are mixed with the acidic mixed solution B.In reactor, add 200 ml deionized water earlier and make end water, adopt the cocurrent adding material mode to neutralize with 8%wt ammonia spirit D, temperature control is at 60～70 ℃, be under the 120r/min and flow to add and carry out neutralization reaction that in the agitator mixing speed pH value is controlled at 7.5～8.5, the reinforced time is about 30 minutes, then add the waterglass 200g solution C that contains silica 1 8%, the reinforced time is that pH value is controlled at 8.5～9.5 about 15 minutes, aging 1 hour.Spend deionised water to the stem-based catalyst chloride ion content less than 0.5%, last is all over being respectively the washing of 0.05%, 0.01% carbonate solution with containing Na, K.Filter cake is crushed to 250 orders through 120 ℃ of oven dry 24 hours.Take by weighing the extrusion aid methylcellulose of the dry glue powder weight 1.0%wt that makes again, the two fully mixes.Mixed siccative is mediated after the rare nitric acid that adds 2%wt is binding agent, and the kneading time is 0.5 hour, uses the banded extruder moulding, is shaped as φ 3mm bar shaped.Drying 12 hours, dry back are calcined down at 500 ℃ and were obtained finished catalyst in 4 hours.Specific surface is 246m
2/ g, pore volume 0.47ml/g; Total acid content is 0.81mmol/g.
Application of Catalyst is carried out in fixed bed, and catalyst places the reactor flat-temperature zone, does supporter with stainless (steel) wire and quartz sand up and down.The Application of Catalyst condition is pressure 0.8-0.9MPa, 320～360 ℃ of temperature, and volume space velocity is 1.0h
-1
Methanol conversion is 85.6% after measured, selectivity 99.1%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 2
Get the aluminum trichloride solution 1000g that contains aluminium 3%wt, get lanthanum nitrate, each 20g of cerous nitrate solution of containing La, Ce5%wt, contain calcium chloride, the magnesium chloride magnesium solution 5g of Ca, Mg3%wt, be mixed with acidic mixed solution under stirring.Neutralize, wear out, wash the stem-based catalyst chloride ion content less than 0.5% with embodiment 1, last is all over being respectively the washing of 0.05%, 0.01% carbonate solution with containing Na, K.Filter cake is crushed to 250 orders through 120 ℃ of oven dry 24 hours.Take by weighing the extrusion aid sesbania gum of the dry glue powder weight 1.5%wt that makes again, the two fully mixes.Mixed siccative is mediated after the rare nitric acid that adds 3%wt is binding agent, and the kneading time is 0.5 hour, uses the banded extruder moulding, is shaped as φ 3mm cloverleaf pattern.Drying 12 hours, dry back are calcined down at 550 ℃ and were obtained finished catalyst in 3 hours.Specific surface is 238m
2/ g, pore volume 0.45ml/g; The acid amount is 0.76mmol/g.
Application of Catalyst is carried out in fixed bed, and catalyst places the reactor flat-temperature zone, does supporter with stainless (steel) wire and quartz sand up and down.The Application of Catalyst condition is pressure 0.8-0.9MPa, 320～360 ℃ of temperature, and volume space velocity is 1.0h
-1
Methanol conversion is 84.6% after measured, selectivity 99.7%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 3
Get the aluminum trichloride solution 1000g that contains aluminium 3%wt, get lanthanum chloride, each 10g of solution of cerium chloride by oxidation of containing La, Ce6%wt, contain Ca, Mg3%wt calcium chloride, magnesium chloride magnesium solution 5g, be mixed with acidic mixed solution under stirring.Neutralize, wear out, wash the stem-based catalyst chloride ion content less than 0.5% with embodiment 1, last is all over being respectively the washing of 0.1%, 0.05% hydroxide solution with containing Na, K.Filter cake is crushed to 250 orders through 120 ℃ of oven dry 24 hours.Take by weighing the extrusion aid sesbania gum of the dry glue powder quality 1.5%wt that makes again, the two fully mixes.Mixed siccative is mediated after the aluminium colloidal sol that adding contains aluminium 3%wt is binding agent, and the addition of aluminium colloidal sol is as the criterion with suitable extrusion molding, and the kneading time is 0.5 hour, uses the banded extruder moulding, is shaped as the bar shaped of φ 2mm.Drying 12 hours, dry back are calcined down at 600 ℃ and were obtained finished catalyst in 2 hours.Specific surface is 217m
2/ g, pore volume 0.48ml/g; The acid amount is 0.87mmol/g.
Application of Catalyst is carried out in fixed bed, and catalyst places the reactor flat-temperature zone, does supporter with stainless (steel) wire and quartz sand up and down.The Application of Catalyst condition is pressure 0.8-0.9MPa, 320～360 ℃ of temperature, and volume space velocity is 1.0h
-1
Methanol conversion is 85.6% after measured, selectivity 99.4%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 4
Get the aluminum nitrate solution 1000g that contains aluminium 3%wt, get lanthanum nitrate, each 15g of cerous nitrate solution of containing La, Ce5%wt, contain Ca, Mg3%wt calcium chloride, magnesium chloride solution 15g, neutralization with embodiment 1 is prepared into glue, aging 3 hours, spend deionised water to stem-based catalyst nitrate ion content less than 1%, last is all over being respectively the washing of 0.08%, 0.05% sodium hydroxide solution with containing Na, K.The Preparation of catalysts method is with embodiment 1.Specific surface is 201m
2/ g, pore volume 0.48ml/g, the acid amount is 1.2mmol/g.
Methanol conversion is 85.6% after measured, selectivity 99.0%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 5
Get the aluminum nitrate solution 1000g that contains aluminium 3%wt, get lanthanum nitrate, each 15g of cerous nitrate solution of containing La, Ce5%wt, contain Ca, Mg3%wt calcium nitrate, magnesium nitrate solution 15g, neutralization with embodiment 1 is prepared into glue, aging 3 hours, spend deionised water to stem-based catalyst nitrate ion content less than 1%, last is all over being respectively 0.5%, 0.1% NaOH, potassium hydroxide solution washing with containing Na, K.The Preparation of catalysts method is binding agent with embodiment 1 with the Ludox that contains silica 5%, and forming method is with example 3.Specific surface is 211m
2/ g, pore volume 0.53ml/g, total acid content are 0.75mmol/g.
Methanol conversion is 85.0% after measured, selectivity 99.7%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 6
Get the aluminum nitrate solution 1000g that contains aluminium 3%wt, get lanthanum nitrate, each 15g of cerous nitrate solution of containing La, Ce5%wt, contain Ca, Mg6%wt calcium chloride, magnesium chloride solution 25g, neutralization with embodiment 1 is prepared into glue, aging 3 hours, spend deionised water to stem-based catalyst chlorine root and nitrate ion content respectively less than 0.4% and 1%, last is all over being respectively 0.1%, 0.05% sodium carbonate, potassium hydroxide solution washing with containing Na, K.The Preparation of catalysts method is binding agent with embodiment 1 with the acetum that contains 5%, and forming method is with example 3.Specific surface is 201m
2/ g, pore volume 0.48ml/g, total acid content are 0.62mmol/g.
Methanol conversion is 85.1% after measured, selectivity 99.3%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 7
Get the aluminum sulfate solution 1500g that contains aluminium 2%wt, get lanthanum nitrate, each 10g of cerous nitrate solution of containing La, Ce5%wt, contain Ca, Mg3%wt calcium nitrate, magnesium nitrate solution 10g, neutralization with embodiment 1 is prepared into glue, aging 2 hours, spend deionised water to the stem-based catalyst sulfate ion content less than 0.5%wt, last is all over being respectively the washing of 0.1%, 0.01% salpeter solution with containing Na, K.Other preparation method of catalyst is with embodiment 1,450 ℃ of calcining heats, and calcination time is 6 hours.Specific surface is 231m
2/ g, pore volume 0.51ml/g, total acid content are 0.88mmol/g.
Methanol conversion is 85.8% after measured, selectivity 99.9%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 8
Get the aluminum sulfate solution 1500g that contains aluminium 2%wt, lanthanum chloride, each 15g of solution of cerium chloride by oxidation of containing La, Ce3%wt, contain Ca, Mg5%wt calcium chloride, magnesium chloride solution 50g, neutralization with embodiment 1 is prepared into glue, aging 2 hours, spend deionised water to the stem-based catalyst sulfate ion content less than 0.5%wt, last is all over being respectively the washing of 0.05%, 0.05% nitrate solution with containing Na, K.Other preparation method of catalyst is with embodiment 1.Specific surface is 231m
2/ g, pore volume 0.51ml/g, total acid content are 0.8mmol/g.
Methanol conversion is 85.2% after measured, selectivity 99.30%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 9
Get the aluminum sulfate solution 1500g that contains aluminium 2%wt, get lanthanum nitrate, each 30g of cerous nitrate solution of containing La, Ce6%wt, contain Ca, Mg6.5%wt calcium nitrate, magnesium nitrate solution 40g, neutralization with embodiment 1 is prepared into glue, aging 2 hours, spend deionised water to the stem-based catalyst sulfate ion content less than 0.5%wt, last is all over being respectively the washing of 0.5%, 0.1% salpeter solution with containing Na, K.Other preparation method of catalyst is with embodiment 1.Specific surface is 243m
2/ g, pore volume 0.48ml/g, the acid amount is 0.67mmol/g.
Methanol conversion is 84.2% after measured, selectivity 99.60%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 10
With containing aluminium 4%wt sodium aluminate solution 750g, get and contain La, the lanthanum nitrate of Ce5%wt, each 15g of cerous nitrate solution, contain Ca, Mg3%wt calcium nitrate, magnesium nitrate solution 15g is made into mixed solution B, with 15% salpeter solution is precipitating reagent, in reactor, add 300 milliliters in water of certain end, pH value 8.0, mixing speed 150r/min, temperature is controlled in 40～50 ℃ of scopes, under pH value 7.5～8.2 conditions, carry out and stream is neutralized into glue, time is 60 minutes, adds the waterglass 200g solution of silica 1 5%, control pH value 8.0～9.0, aging 2 hours, more after filtration, deionized water washing some all over Na ion to stem-based catalyst less than 1.0%wt.The moulding activated mode of catalyst is with embodiment 1,650 ℃ of calcining heats, and calcination time is 3 hours.Specific surface is 216m
2/ g, pore volume 0.50ml/g, total acid content are 0.83mmol/g.
Methanol conversion is 86.4% after measured, selectivity 99.2%; Under 400 ℃, two hours crystalline phases of 1.0MPa steam treatment are stable.
Embodiment 11
With containing aluminium 4%wt sodium aluminate solution 750g.Contain La, the lanthanum chloride of Ce5%wt, each 15g of solution of cerium chloride by oxidation, contain Ca, Mg3%wt calcium chloride, magnesium chloride solution 15g is made into mixed solution B, carbon dioxide is a precipitating reagent, in reactor, add 300 milliliters in water of certain end, pH value 8.0, mixing speed 300r/min, temperature is controlled in 20～40 ℃ of scopes, adds sodium aluminate solution, slowly add mixed solution B, logical people's carbon dioxide is neutralized into glue, and the time is 80 minutes, the waterglass 200g solution that adds silica 1 5%, control terminal point pH value 7.5～8.0, aging 1.5 hours, more after filtration, deionized water washing some all over Na ion to stem-based catalyst less than 1.0%wt.The moulding activated mode of catalyst is with embodiment 1.Specific surface is 230m
2/ g, pore volume 0.48ml/g, the acid amount is 0.85mmol/g.
Methanol conversion is 85.3% after measured, selectivity 99.6%.400 ℃, two hours crystalline phases of steam treatment are stable under the 1.0MPa.
Embodiment 12
With containing aluminium 4%wt sodium aluminate solution 750g.Contain La, the lanthanum chloride of Ce5%wt, each 30g of solution of cerium chloride by oxidation, contain Ca, Mg6%wt calcium chloride, magnesium chloride solution 40g is made into mixed solution B, 18% sulfuric acid is precipitating reagent, in reactor, add 300 milliliters in water of certain end, pH value 8.0, mixing speed 300r/min, temperature is controlled in 60～80 ℃ of scopes, adds sodium aluminate solution, slowly adds mixed solution B, be neutralized into glue, time is 80 minutes, adds the water glass solution 200g of silica 1 5%, control terminal point pH value 7.5～8.0, aging 1.5 hours, more after filtration, deionized water washing some all over Na ion to stem-based catalyst less than 1.0%wt.With the aluminium colloidal sol that contains aluminium 4%wt is binding agent, and shaping of catalyst prepares with example 3,400 ℃ of calcining heats, and calcination time is 5 hours.Specific surface is 260m
2/ g, pore volume 0.52ml/g, the acid amount is 0.91mmol/g.
Methanol conversion is 84.6% after measured, selectivity 99.7%.400 ℃, two hours crystalline phases of steam treatment are stable under the 1.0MPa.
Claims (10)
1. preparing dimethyl ether by dewatering methanol catalyst, it is characterized in that: finished catalyst each component percentage by weight consists of:
Al
2O
3：35～95％；
SiO
2： 1～50％；
La： 0.1～5％；
Ce： 0.1～5％；
Ca： 0.1～3％；
Mg： 0.1～3％；
Na： 0.01～1％；
K： 0.01～1％；
Specific surface is 150～380m
2/ g, pore volume are 0.3～1.0ml/g; The acid amount is controlled at 0.1～1.5mmol/g.
2. preparing dimethyl ether by dewatering methanol catalyst as claimed in claim 1, it is characterized in that: the each component percentage by weight consists of:
Al
2O
3：80～90％；
SiO
2： 5～15％；
La： 0.5～2％；
Ce： 0.5～2％；
Ca： 0.1～1％；
Mg： 0.1～1％；
Na： 0.1～0.6％；
K： 0.01～0.5％；
Specific surface is 180～240m
2/ g, pore volume are 0.4～0.7ml/g.
3. preparing dimethyl ether by dewatering methanol as claimed in claim 1 Preparation of catalysts method is characterized in that:
Be divided into two kinds of routes according to different aluminium sources:
The preparation of dry glue powder I:
A. prepare aluminum salt solution A, slowly adding contains La, Ce, Ca, Mg are the solution of auxiliary agent, make mixed solution B; Preparing silica containing silicon source is solution C; Ammonia spirit is a solution D;
B. in reactor, add water of certain end, stir;
C. under the condition of pH value 7.3～8.5, solution A, solution B and solution D are carried out earlier and stream is neutralized into glue, add solution C, and pH value 7～10 is aging;
D. more after filtration, deionized water washs to the stem-based catalyst acid ion less than 1.0%wt;
E. last with the solution washing that contains Na, K, the filter cake drying is pulverized and is made catalyst dry glue powder I;
The preparation of dry glue powder II:
A. prepare aluminum salt solution E earlier; And handle contains La, Ce, Ca, Mg are the solution of auxiliary agent, make mixed solution B; Preparing silica containing silicon source is solution C; Salpeter solution or sulfuric acid solution are solution F; Carbon dioxide is neutralization medium G;
B. in reactor, add water of certain end, stir;
C. under the condition of pH value 7～9, solution E, solution C, solution B and solution F or neutralization medium G carry out and stream is neutralized into glue, and be aging;
D. more after filtration, deionized water washing some all over Na ion to stem-based catalyst less than 1.0%wt;
E. the filter cake drying is pulverized and is made catalyst dry glue powder II;
The moulding of methanol dehydration catalyst is to take by weighing a certain amount of dry glue powder I or II, takes by weighing extrusion aid again, and the two fully mixes; Mixed siccative is mediated after adding binding agent, moulding then, drying, and the calcining of dry back obtains finished catalyst.
4. Preparation of catalysts method as claimed in claim 3, wherein:
Aluminum salt solution among the preparation process a of dry glue powder I is alchlor, aluminum sulfate, aluminum nitrate solution, contains aluminium 1～6%wt;
Aluminum salt solution among the preparation process a of dry glue powder II is a sodium aluminate solution, contains aluminium 1～6%wt.
5. Preparation of catalysts method as claimed in claim 3, wherein: the solution that contains La, Ce, Ca, Mg and be auxiliary agent is selected from one or more in salpeter solution, sulfuric acid solution or the hydrochloric acid solution that contains La, Ce, Ca, Mg; Each composition weight percentage composition is: La:0.1～5%; Ce:0.1～5%; Ca:0.1～3%; Mg:0.1～3%; Na:0.01～1%; K:0.01～1%.
6. Preparation of catalysts method as claimed in claim 3, wherein: the each component percentage by weight consists of: La:0.5～2%; Ce:0.5～2%; Ca:0.1～1%; Mg:0.1～1%; Na:0.1～0.6%; K:0.01～0.5%.
7. Preparation of catalysts method as claimed in claim 3, wherein: the silicon source is waterglass or Ludox, contains silica 3～20%wt.
8. Preparation of catalysts method as claimed in claim 3, wherein: the solution that contains Na, K among the preparation process e of dry glue powder I is selected from sodium nitrate, sodium carbonate or sodium hydroxide solution, and Na, K concentration are 0.01%～0.5%wt.
9. one kind as any one preparing dimethyl ether by dewatering methanol Preparation of catalysts method as described in the claim 3～8, and wherein: extrusion aid is selected from methylcellulose or sesbania gum, concentration 0.5～2.0%wt.
10. one kind as any one preparing dimethyl ether by dewatering methanol Preparation of catalysts method as described in the claim 3～8, and wherein: binding agent is rare nitric acid, spirit of vinegar, aluminium colloidal sol or the Ludox of 1%～6%wt, and the kneading time is not less than 0.5 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101034369A CN100379491C (en) | 2006-07-21 | 2006-07-21 | Catalyst for preparing dimethyl ether by methanol dehydration and its preparation method |
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|---|---|---|---|
| CNB2006101034369A CN100379491C (en) | 2006-07-21 | 2006-07-21 | Catalyst for preparing dimethyl ether by methanol dehydration and its preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453169C (en) * | 2007-09-29 | 2009-01-21 | 中国科学院山西煤炭化学研究所 | Catalyst for producing dimethyl ether and its preparation method and application |
| CN101786014A (en) * | 2010-03-05 | 2010-07-28 | 南开大学 | Catalyst for preparing dimethyl ether by dehydration of methanol, and application thereof |
| CN101380585B (en) * | 2007-09-07 | 2011-07-27 | 新奥科技发展有限公司 | Wide temperature type methanol dehydration catalyst for producing dimethyl ether and preparation method thereof |
| CN105233832A (en) * | 2015-11-09 | 2016-01-13 | 华东理工大学 | Composite catalyst for preparing dimethyl ether from synthesis gas through one-step method and preparing method thereof |
| CN105688946A (en) * | 2016-03-02 | 2016-06-22 | 济南大学 | Solid acid catalyst and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550067B (en) * | 2009-05-15 | 2013-03-20 | 新奥新能(北京)科技有限公司 | Method for producing two-stage dimethyl ether |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK373784A (en) * | 1983-06-16 | 1986-02-02 | Du Pont | METHOD AND CATALYST FOR PRODUCING DIMETHYLETHER |
| CN1524618A (en) * | 2003-09-17 | 2004-09-01 | 中国石化集团南京化学工业有限公司催 | Catalyst for synthesis of dimethyl ether in fluid bed |
| CN1613558A (en) * | 2004-10-12 | 2005-05-11 | 南京大学 | Modified alumina catalyst for synthetizing dimethyl ether |
| CN100500285C (en) * | 2005-08-11 | 2009-06-17 | 中国科学院山西煤炭化学研究所 | Catalyst, production and use for producing dimethyl ether by dewatering methanol |
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2006
- 2006-07-21 CN CNB2006101034369A patent/CN100379491C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380585B (en) * | 2007-09-07 | 2011-07-27 | 新奥科技发展有限公司 | Wide temperature type methanol dehydration catalyst for producing dimethyl ether and preparation method thereof |
| CN100453169C (en) * | 2007-09-29 | 2009-01-21 | 中国科学院山西煤炭化学研究所 | Catalyst for producing dimethyl ether and its preparation method and application |
| CN101786014A (en) * | 2010-03-05 | 2010-07-28 | 南开大学 | Catalyst for preparing dimethyl ether by dehydration of methanol, and application thereof |
| CN105233832A (en) * | 2015-11-09 | 2016-01-13 | 华东理工大学 | Composite catalyst for preparing dimethyl ether from synthesis gas through one-step method and preparing method thereof |
| CN105688946A (en) * | 2016-03-02 | 2016-06-22 | 济南大学 | Solid acid catalyst and preparation method and application thereof |
| CN105688946B (en) * | 2016-03-02 | 2018-05-04 | 济南大学 | A kind of solid acid catalyst and its preparation method and application |
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| CN100379491C (en) | 2008-04-09 |
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