CN104857953A - Preparation method of catalyst for manufacturing propylene by disproportionating carbon four and ethylene - Google Patents
Preparation method of catalyst for manufacturing propylene by disproportionating carbon four and ethylene Download PDFInfo
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- CN104857953A CN104857953A CN201510230108.4A CN201510230108A CN104857953A CN 104857953 A CN104857953 A CN 104857953A CN 201510230108 A CN201510230108 A CN 201510230108A CN 104857953 A CN104857953 A CN 104857953A
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Abstract
The invention discloses a preparation method of a catalyst for manufacturing propylene by disproportionating carbon four and ethylene. The preparation method mainly includes the steps: firstly, manufacturing a KIT-6 or P-doped KIT-6 carrier; secondly, dipping the carrier in rhenium soluble salt solution and tungsten soluble salt solution and then dipping the carrier in vanadium salt solution or niobium salt solution or tantalum salt solution by a stepwise dipping method; finally, drying, calcining and reducing the carrier to obtain the catalyst. Compared with an existing catalyst for manufacturing propylene by disproportionating carbon four and ethylene, the prepared catalyst has the advantages of high activity, low cost, long service life and environmental friendliness.
Description
technical field:
The present invention relates to chemical industry synthesis field, particularly relate to a kind of preparation method of the catalyst for carbon four and ethene disproportionation propylene.
background technology:
Propylene extensively uses the multiple important Organic Chemicals such as propane, acetone and fine chemicals, is one of fastest-rising basic chemical raw materials of current worldwide petrochemical market demand.Reach 5.3% in the year demand growth of 1991-2000 propylene according to statistics, exceeded the demand (4.5%) of the ethene same period, the propylene aggregated capacity of China in 2010 is 1,050 ten thousand tons, and propylene consumption figure is 1,905 ten thousand tons, and breach reaches 8,250,000 tons.2008-2013 China propylene growth rate of demand is 10.8%, and the average annual growth of China's propone output is 9.4%.Although propylene production capacity increases year by year, but still far below the actual needs of propylene, supply and demand gap is expanding year by year, is badly in need of the propylene Yield Increase Way that exploitation is new.Utilize the cross disproportionation effect of carbon four and ethene, by adding appropriate ethene, by relative surplus, C4 olefin feedstock that added value is lower is converted into high added value propylene product.The advantage of olefin(e) disproportionation technique is that such technology can combine with traditional technology for Increasing Propylene Yield, and without the need to transforming greatly existing technique, carbon four raw material is easy to get, and cost is low, and application prospect is very extensive.
Within the scope of the world today, Lummus company adopts OCT C4 disproportionated reaction technique, and this technique is to adopt MgO and WO
3/ SiO
2mixed catalyst take fixed bed as reactor, first by MgO catalyst generation isomerization reaction, and then by load WO over celite
3carry out disproportionated reaction and prepare propylene.The olefin(e) disproportionation technique of BASF AG adopts carbon four and alkane producing propylene with dismutation, and its maximum feature is that ethene uses less.Catalyst uses Re
2o
7/ Al
2o
3or WO
3/ SiO
2, the conversion ratio of carbon four is greater than 60%.BSAF mature technology degree is low, also not industrialization completely.CN 1611297A reports a kind of method of adding copper or other oxide technique schemes in oxidation tungsten/silicon dioxide catalyst system and catalyzing and carries out the research that butylene and ethene disproportionation prepare propylene.CN 103272581A discloses a kind of mixture with tungsten oxide, molybdenum oxide and the rhenium oxide composition catalyst that is active component, prepare propylene for ethene and butylene disproportionation, its catalyst efficiency is higher than 70%, propylene selective higher than 80%.
On the whole, what current ethene and butylene disproportionation reaction prepared that the catalyst of propylene all adopts is heterogeneous catalysis system, mainly concentrates on tungsten base, molybdenum base and rhenium-based catalyst, although wherein the anti-poisoning capability of tungsten-based catalyst is strong, but reaction temperature is low, and butene conversion is not high.Molybdenum base and rhenium-based catalyst butene conversion high, reaction temperature is low, but catalyst stability is poor, therefore, urgently develops that butene conversion is high, reaction temperature is low, the catalyst of good stability.
summary of the invention:
The invention provides a kind of preparation method of new catalyst to solve the problem, obtained a kind of catalyst for ethene and carbon four disproportionation propylene, described catalyst is made up of active component, auxiliary agent and carrier.
Described active component is the mixture of rhenium and tungsten oxide, and wherein the quality of the oxide of rhenium is 5 ~ 20% of carrier quality, and the quality of the oxide of tungsten is preferably 2 ~ 6% of carrier quality; .The oxide of rhenium is main catalyst, and the oxide of tungsten is chief active auxiliary agent, plays the effect improving catalyst stability.
Described auxiliary agent is the one in vanadium, niobium and tantalum, and the quality of Qi Zhongfan, niobium and tantalum is preferably 0.1 ~ 1% of carrier quality.
Described carrier is the KIT-6 of KIT-6 and the P modification of three-dimensional cubic pore structure, and its specific area is 400 ~ 700 m2/g, and aperture is that 2 ~ 10 nm are controlled.Regulated the acidic site of carrier surface by P modification, strengthen strong interaction between catalyst and carrier, improve the activity and selectivity of catalyst.
Described preparation method adopts the KIT-6 carrier of first obtained KIT-6 or doping P, adopt step impregnation method again, first the soluble salt solutions of rhenium and the soluble salt solutions of tungsten are impregnated on carrier, again by the salt solution impregnation of the salting liquid of vanadium or the salting liquid of niobium or tantalum on carrier, obtained finally by drying, calcining and reduction, its concrete steps are as follows:
(1) at 35 DEG C, a certain amount of block copolymer P123 is dissolved in a certain amount of deionized water and concentrated hydrochloric acid mixed solution, and after adding a certain amount of n-butanol stirring 1h, be added dropwise to the dibastic sodium phosphate solution of a certain amount of TEOS and 0.1 mol/L, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, the KIT-6 carrier of obtained doping P.
(2) by step (1) gained carrier impregnation in the soluble salt solutions of certain density rhenium and tungsten, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain the mixture of the KIT-6 carrier of the oxide of rhenium-containing, the oxide of tungsten and doping P.
(3) methanol aqueous solution of the soluble-salt of the soluble-salt of certain density vanadium or the soluble-salt of niobium or tantalum is sprayed at uniformly on the mixture obtained in step (3), then at the temperature of 120 DEG C dry 12 hours, at 550 DEG C, roasting obtained described catalyst in 4 hours.
As preferably, do not add dibastic sodium phosphate solution in step (1) and then obtain KIT-6 carrier.
As preferably, the mol ratio of described silicon source and template is: n (TEOS): n (P123)=1:0.05-1:1.
As preferably, described solubility rhenium salt is ammonium perrhenate or perrhenic acid, and tungsten salt is ammonium metatungstate or ammonium tungstate.
As preferably, described solubility vanadic salts is ammonium metavanadate, and niobium salt is columbium pentachloride, and tantalum salt is tantalic chloride.
As preferably, the methanol aqueous solution of the vanadic salts in described step (3), niobium salt or tantalum salt, the volume ratio of methyl alcohol and water is V methyl alcohol: V water=1:10.
Compared with prior art, preparation method of the present invention is adopted to have the following advantages:
1, the catalyst that preparation method of the present invention obtains adopts double activated component, give full play to respective advantage, rhenium-based catalyst activity is high, but anti-poisoning capability is low, tungsten-based catalyst desired reaction temperature is high, but there is strong anti-poisoning capability, the feature of the comprehensive rhenium of the present invention and tungsten, adopt double activated component.
2, preparation method of the present invention adopts and carrys out by doping P the acidic site that modification regulates carrier surface, strengthens strong interaction between catalyst and carrier, improves the activity and selectivity of catalyst.
3, the KIT-6 carrier of the KIT-6 carrier that obtains of preparation method of the present invention or doping P has three-dimensional cubic pore structure, and specific area is large, and aperture is adjustable, and active component can be made to be uniformly dispersed.
detailed description of the invention:
case study on implementation 1
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 1.6129 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, KIT-6 carrier 5 g { n (TEOS): n (the P123)=1:1} of doping P element; Wherein the quality of P element accounts for 0.1% of the KIT-6 carrier gross mass of doping P element.
(2) take 0.5537 g ammonium perrhenate and 0.1064g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.1%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality is 10%, WO3 quality of the KIT-6 carrier gross mass of doping P element is 2% of the KIT-6 carrier gross mass of doping P element.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the ammonium metavanadate of 1.0989 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C.Re in described catalyst
2o
7quality is 10%, WO3 quality of the KIT-6 carrier gross mass of doping P element is 2%, V of the KIT-6 carrier gross mass of doping P element
2o
5quality be 0.1% of the KIT-6 carrier gross mass of doping P element, the quality of P element accounts for 0.1% of the KIT-6 carrier gross mass of doping P element.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-V
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g alumina ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 73%, Propylene Selectivity: 89%.
case study on implementation 2
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 9.6774 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, KIT-6 carrier { n (TEOS): n (the P123)=1:1} of the doping P element of 5 g; Wherein the quality of P element is 0.6% of the KIT-6 carrier gross mass of doping P element.
(2) take 0.8309g ammonium perrhenate and 0.1064g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.1%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality be doping P element KIT-6 carrier gross mass 15%, WO
3quality be doping P element KIT-6 carrier gross mass 2%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the ammonium metavanadate of 1.0989 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C, Re in described catalyst
2o
7quality be doping P element KIT-6 carrier gross mass 15%, WO
3quality be doping P element KIT-6 carrier gross mass 2%, V
2o
5quality be 0.1% of the KIT-6 carrier gross mass of doping P element, the quality of P element is 0.6% of the KIT-6 carrier gross mass of doping P element.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-V
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 84%, Propylene Selectivity: 93%.
case study on implementation 3
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 9.6774 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, KIT-6 carrier { n (TEOS): n (the P123)=1:1} of the doping P element of 5 g; Wherein the quality of P element is 0.6% of the KIT-6 carrier gross mass of doping P element.
(2) take 0.2769g ammonium perrhenate and 0.1064g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.1%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be doping P element KIT-6 carrier gross mass 2%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the ammonium metavanadate of 1.0989 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C.Re in described catalyst
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be 2% of the KIT-6 carrier gross mass of doping P element, the quality of P element is 0.6%, V of the KIT-6 carrier gross mass of doping P element
2o
5quality is 0.1% of the KIT-6 carrier gross mass of doping P element.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-V
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 50%, Propylene Selectivity: 73%.
case study on implementation 4
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 9.6774 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, and { n (TEOS): n (P123)=1:1}, wherein the quality of P element is 0.6% of the KIT-6 carrier gross mass of doping P element to the KIT-6 carrier of the doping P element of 5 g.
(2) take 0.8309g ammonium perrhenate and 0.3187g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.6%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality be doping P element KIT-6 carrier gross mass 15%, WO
3quality be doping P element KIT-6 carrier gross mass 6%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the ammonium metavanadate of 9.8901 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst, wherein Re at 550 DEG C
2o
7re
2o
7quality be doping P element KIT-6 carrier gross mass 15%, WO
3quality be 6% of the KIT-6 carrier gross mass of doping P element, the quality of P element is 0.6%, V of the KIT-6 carrier gross mass of doping P element
2o
5quality be doping P element KIT-6 carrier gross mass 0.9%.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-V
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 80 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 80%, Propylene Selectivity: 92%.
case study on implementation 5
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 14.52 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, and { n (TEOS): n (P123)=1:1}, wherein the quality of P element is 0.9% of the KIT-6 carrier gross mass of doping P element to the KIT-6 carrier of the doping P element of 5 g.
(2) take 1.1075g ammonium perrhenate and 0.2125g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.9%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality be doping P element KIT-6 carrier gross mass 20%, WO
3quality be doping P element KIT-6 carrier gross mass 4%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the ammonium metavanadate of 9.8901 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C.Re in described catalyst
2o
7quality be doping P element KIT-6 carrier gross mass 20%, WO
3quality be 4% of the KIT-6 carrier gross mass of doping P element, the quality of P element is 0.9%, V of the KIT-6 carrier gross mass of doping P element
2o
5quality be doping P element KIT-6 carrier gross mass 0.9%.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-V
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 80 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 78%, Propylene Selectivity: 88%.
case study on implementation 6
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 9.6774 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, KIT-6 carrier { n (TEOS): n (the P123)=1:1} of the doping P element of 5 g; Wherein the quality of P element is 0.6% of the KIT-6 carrier gross mass of doping P element.
(2) take 0.2769g ammonium perrhenate and 0.1064g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.1%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be doping P element KIT-6 carrier gross mass 2%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the columbium pentachloride of 0.7524 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C, Re in described catalyst
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be 2% of the KIT-6 carrier gross mass of doping P element, the quality of P element is 0.6%, Nb of the KIT-6 carrier gross mass of doping P element
2o
5quality be doping P element KIT-6 carrier gross mass 0.1%.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-Nb
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 53%, Propylene Selectivity: 73%.
case study on implementation 7
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 9.6774 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, and { n (TEOS): n (P123)=1:1}, wherein the quality of P element is 0.6% of the KIT-6 carrier gross mass of doping P element to the KIT-6 carrier of the doping P element of 5 g.
(2) take 0.2769g ammonium perrhenate and 0.1064g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.1%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be doping P element KIT-6 carrier gross mass 2%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the tantalic chloride of 0.4526 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C, Re in described catalyst
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be 2% of the KIT-6 carrier gross mass of doping P element, the quality of P element is 0.6%, Ta of the KIT-6 carrier gross mass of doping P element
2o
5quality be doping P element KIT-6 carrier gross mass 0.1%.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-Ta
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 55%, Propylene Selectivity: 78%.
case study on implementation 8
(1) at 35 DEG C, 4.26g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 9.6774 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 600 m
2/ g, aperture is 7nm, and { n (TEOS): n (P123)=1:0.5}, wherein the quality of P element is 0.6% of the KIT-6 carrier gross mass of doping P element to the KIT-6 carrier of the doping P element of 5 g.
(2) take 0.2769g ammonium perrhenate and 0.1064g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.1%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be doping P element KIT-6 carrier gross mass 2%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the tantalic chloride of 0.4526 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C.Re in described catalyst
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be 2% of the KIT-6 carrier gross mass of doping P element, the quality of P element is 0.6%, Ta of the KIT-6 carrier gross mass of doping P element
2o
5quality be doping P element KIT-6 carrier gross mass 0.1%.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-Ta
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 50%, Propylene Selectivity: 72%.
case study on implementation 9
(1) at 35 DEG C, 0.8520g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 9.6774 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 400 m
2/ g, aperture is 2 nm, and { n (TEOS): n (P123)=1:0.1}, wherein the quality of P element is 0.6% of the KIT-6 carrier gross mass of doping P element to the KIT-6 carrier of the doping P element of 5 g.
(2) take 0.2769g ammonium perrhenate and 0.1064g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.1%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials of doping P element, wherein Re
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be doping P element KIT-6 carrier gross mass 2%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the tantalic chloride of 0.4526 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C, Re in described catalyst
2o
7quality be doping P element KIT-6 carrier gross mass 5%, WO
3quality be 2% of the KIT-6 carrier gross mass of doping P element, the quality of P element is 0.6%, Ta of the KIT-6 carrier gross mass of doping P element
2o
5quality be doping P element KIT-6 carrier gross mass 0.1%.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-Ta
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 45%, Propylene Selectivity: 68%.
case study on implementation 10
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and be added dropwise to 17.36 g TEOS after adding 8g n-butanol stirring 1h, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, KIT-6 carrier { n (TEOS): n (the P123)=1:1} of 5 g.
(2) take 0.8309g ammonium perrhenate and 0.1064g ammonium metatungstate to be dissolved in 20 ml deionized waters and to mix, and by 5 g KIT-6 carrier impregnation obtained in step (1) in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain containing Re
2o
7, WO
3with the mixture of KIT-6 carrier three kinds of materials, wherein Re
2o
7quality be 15%, WO of KIT-6 carrier gross mass
3quality be 2% of KIT-6 carrier gross mass.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the ammonium metavanadate of 1.0989 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained catalyst at 550 DEG C, Re in described catalyst
2o
7quality be 15%, WO of KIT-6 carrier gross mass
3quality be 2%, V of KIT-6 carrier gross mass
2o
5quality be 0.1% of KIT-6 carrier gross mass.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-V
2o
5-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene and carbon four from reactor upper end, ethene flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 75%, Propylene Selectivity: 81%.
case study on implementation 11
(1) at 35 DEG C, 8g block copolymer P123 is dissolved in 290.5g deionized water and 15.8g 35% concentrated hydrochloric acid mixed solution, and adds the Na being added dropwise to 0.1 mol/L of 17.36 g TEOS and 9.6774 ml after 8g n-butanol stirs 1h
2hPO
4solution, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, and obtained specific area is 700 m
2/ g, aperture is 10 nm, KIT-6 carrier { n (TEOS): n (the P123)=1:1} of the doping 0.6%P element of 5 g.
(2) take 0.7779g perrhenic acid and 0.1094g ammonium tungstate to be dissolved in 20 ml deionized waters and to mix, and the KIT-6 carrier impregnation of the 0.1%P element that adulterated by 5 g obtained in step (1) is in prepared solution, through 120 DEG C of dryings, 550 DEG C of roastings, after 4 hours, obtain Re
2o
7content is 15wt%, WO
3content is 2wt%, and P element content is the KIT-6 mixture of 0.6wt%.
(3) methanol aqueous solution (V methyl alcohol: V water=1:10) of the ammonium metavanadate of 1.0989 ml 0.05mol/L is taken, it is sprayed at uniformly on the mixture of preparation in step (2), drying 12 hours at the temperature of 120 DEG C, roasting 4 hours obtained Re at 550 DEG C
2o
7content is 15wt%, WO
3content is 2wt%, and P element content is 0.1wt%, V
2o
5content is the KIT-6 catalyst of 0.1wt%.
(4) be 50cm in length, bottom the stainless steel reactor of internal diameter 1cm, add 2g alumina ball filler; By the Re of preparation in above-mentioned steps (3)
2o
7-WO
3-V
2o
5-P-KIT-6 shaping of catalyst joins reactor well, 2g Aluminum Oxide Aluminum oxide porcelain ball filler is loaded in upper end, then in reactor, high pure nitrogen is passed through, flow velocity is 50 ml/min, after checking air-tightness, temperature of reactor is elevated to 550 DEG C, heating rate is 1 DEG C/min, constant temperature 4h, then is cooled to 100 DEG C, stop passing into nitrogen, pass into ethene from reactor upper end, flow velocity is 20 ml/min, and carbon four flow velocity is that 10 ml/min carry out catalytic reaction, react and reach balance after 2 hours, product is by the on-line analysis of southern Shandong GC2060 gas-chromatography.
Experimental result: carbon four conversion ratio: 83.5%, Propylene Selectivity: 93%.
Below to invention has been detailed description, but the present invention is not limited to detailed description of the invention described herein.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and distortion can be made.Protection scope of the present invention is defined by the following claims.
Claims (6)
1. the preparation method for the catalyst of carbon four and ethene disproportionation propylene, described catalyst comprises active component, auxiliary agent and carrier, described active component is the oxide of rhenium and the hopcalite of tungsten, wherein the quality of the oxide of rhenium is 5 ~ 20% of carrier quality, and the quality of the oxide of tungsten is 2 ~ 6% of carrier quality; Described auxiliary agent is the one in barium oxide, niobium oxide or tantalum pentoxide, and its quality is 0.1 ~ 0.9% of carrier quality; Described carrier is the KIT-6 of KIT-6 or P modification, in the KIT-6 of P modification, the quality of P accounts for 0.1 ~ 0.9% of the KIT-6 carrier gross mass of P modification, it is characterized in that, this catalyst adopts the KIT-6 carrier of first obtained KIT-6 or doping P, adopt step impregnation method again, first the soluble salt solutions of rhenium and the soluble salt solutions of tungsten are impregnated on carrier, again by the salt solution impregnation of the salting liquid of vanadium or the salting liquid of niobium or tantalum on carrier, obtained finally by drying, calcining and reduction, its concrete steps are as follows:
(1) at 35 DEG C, a certain amount of block copolymer P123 is dissolved in a certain amount of deionized water and concentrated hydrochloric acid mixed solution, and after adding a certain amount of n-butanol stirring 1h, be added dropwise to the dibastic sodium phosphate solution of a certain amount of TEOS and 0.1 mol/L, continue at the same temperature to stir 24h, the mixed solution of gained being transferred to polytetrafluoroethylene (PTFE) is in the reactor of liner, hydro-thermal reaction 24h at 100 DEG C, deionized water is spent after being cooled to room temperature, until pH value of solution is neutral, then at 100 DEG C, drying obtains pressed powder, finally by the pressed powder of gained in Muffle furnace with 1 DEG C of min
-1heating rate be heated to 550 DEG C, at 550 DEG C, calcining at constant temperature 4h is to remove organic formwork agent, the KIT-6 carrier of obtained doping P,
(2) by carrier impregnation obtained in step (1) in the soluble salt solutions of certain density rhenium and tungsten, through 120 DEG C of dryings, 550 DEG C after roasting 2-6 hour, obtain the mixture of the KIT-6 carrier of the oxide of rhenium-containing, the oxide of tungsten and doping P;
(3) methanol aqueous solution of the soluble-salt of the soluble-salt of certain density vanadium or the soluble-salt of niobium or tantalum is sprayed at uniformly on the mixture obtained in step (3), then at the temperature of 120 DEG C dry 12 hours, at 550 DEG C, roasting obtained described catalyst in 4 hours.
2. the preparation method of a kind of catalyst for carbon four and ethene disproportionation propylene according to claim 1, is characterized in that, in described step (1), not add dibastic sodium phosphate solution, then obtained product is KIT-6 carrier.
3. the preparation method of a kind of catalyst for carbon four and ethene disproportionation propylene according to claim 1 and 2, it is characterized in that: in described step (1), the mol ratio of silicon source and template is: n (TEOS): n (P123)=1:0.05-1:1.
4. the preparation method of a kind of catalyst for carbon four and ethene disproportionation propylene according to claim 1 and 2, it is characterized in that, in described step (2), solubility rhenium salt is ammonium perrhenate or perrhenic acid, and soluble tungsten salt is ammonium metatungstate or ammonium tungstate.
5. the preparation method of a kind of catalyst for carbon four and ethene disproportionation propylene according to claim 1 and 2, it is characterized in that, the solubility vanadic salts in described step (3) is ammonium metavanadate, and niobium salt is columbium pentachloride, and tantalum salt is tantalic chloride.
6. the preparation method of a kind of catalyst for carbon four and ethene disproportionation propylene according to claim 1 and 2, it is characterized in that, the methanol aqueous solution of the vanadic salts in described step (3), niobium salt or tantalum salt, the volume ratio of methyl alcohol and water is V methyl alcohol: V water=1:10.
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