CN105152834A - Method for continuous preparation of olefin and aromatic hydrocarbon by microchannel reactor - Google Patents
Method for continuous preparation of olefin and aromatic hydrocarbon by microchannel reactor Download PDFInfo
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- CN105152834A CN105152834A CN201510303990.0A CN201510303990A CN105152834A CN 105152834 A CN105152834 A CN 105152834A CN 201510303990 A CN201510303990 A CN 201510303990A CN 105152834 A CN105152834 A CN 105152834A
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Abstract
The invention discloses a method for continuous preparation of olefin and aromatic hydrocarbon by a microchannel reactor. The method comprises, 1, under the action of carrying gas N2, feeding bromomethane into a microchannel reactor with a catalyst, and carrying out a catalytic reaction process at a temperature of 100-500 DEG C, 2, cooling and collecting the reaction mixture to obtain olefin and aromatic hydrocarbon, 3, feeding the produced hydrogen bromide into a channel with a metal oxide to obtain a metal bromide, and feeding oxygen into the metal bromide to obtain a metal oxide and bromine, and 4, recycling the produced metal oxide for the step 3, and storing the produced bromine as a bromine source of bromomethane preparation from methane. Through olefin and aromatic hydrocarbon synthesis from bromomethane in the microchannel and recovery and recycle of by-product hydrogen bromide produced by the reaction process, equipment corrosion and environmental pollution are reduced and the novel olefin and aromatic hydrocarbon preparation method and gas resource comprehensive utilization are realized.
Description
Technical field
A kind of method that the present invention relates to continuous production alkene and aromatic hydrocarbons in micro passage reaction belongs to the technical field of Chemical Manufacture preparation method.
Background technology
The chemical utilization of Sweet natural gas is broadly divided into direct method and indirect method two kinds.Direct method as directly oxidizing methane methyl alcohol, formaldehyde and coupling ethene etc., although these processes through long-term effort research, due to object product under severe reaction conditions (high temperature, high pressure), being easy to deep oxidation is CO
2and H
2o, yield and selectivity lower, can't compete mutually with traditional petrochemical process at present, be difficult in a short time realize industrialization.Therefore, the indirect reformer of Sweet natural gas utilizes the emphasis again becoming countries in the world research in recent years.Wherein, utilize Sweet natural gas to be first converted into synthetic gas and prepare ammonia, methyl alcohol, liquid fuel etc. again and achieved large-scale commercial production, in Chemical Manufacture, occupy dominant position.But due to the complex manufacturing of synthetic gas, facility investment is huge, the shortcomings such as process cost is expensive, impel countries in the world to make great efforts to explore new indirect reformer approach.
Because halomethane can be converted into the Chemicals of the high added values such as alcohols, ethers, alkene, high-carbon hydrocarbon, aromatic hydrocarbons efficiently, be subject to the extensive concern of chemist.1985, the people such as Olah reported methane and chlorine (or hydrogenchloride) under oxygen existence condition, load type metal Pt catalyzer can be obtained by reacting methyl chloride, then be that intermediate obtains the Chemicals such as methyl alcohol, high-carbon hydrocarbon with methyl chloride.1988, the people such as Taylor reported methane and are converted into methyl chloride by oxychlorination reaction, then take off HCl by methyl chloride and obtain high-carbon hydrocarbon, and wherein HCl recycles in reactive system, makes reaction process both economical.But methyl chloride thermal discharge in preparation process is large, reacts wayward, be separated relatively difficulty, and methyl chloride activate difficulty compared with monobromethane wants greatly, limit its application prospect industrially.
The people such as Lorkovic take metal bromide as catalyzer, at O
2effect under three-step approach oxidative coupling methane for high-carbon hydrocarbon.The first step passes into O in the metal bromide of load on solid
2, have Br in this course
2simple substance and corresponding metal oxide generate.Second step reaction is by the Br of previous step
2simple substance and excessive methane reaction, generate monobromethane and hydrogen bromide in this step.Finally, the monobromethane of generation and hydrogen bromide and unreacted methane are passed into load to be had in the molecular sieve of metal oxide, is converted to product by high efficiency for monobromethane.Meanwhile, hydrogen bromide and metal oxide generate metal bromide and water, and the metal bromide of generation can continue catalyzed reaction as the catalyzer of monobromethane linked reaction and carry out.Week, little equality people have studied with HBr and O
2as medium, bromination is carried out to methane and generate CH
3br and CH
2br
2, then generate the high-carbon hydrocarbons such as alkene with catalyst action.Because the temperature of reaction in these prior synthesizing method is general higher, catalyzer coking is fast, and easy inactivation, is unfavorable for industrial applications.And adopt micro passage reaction, the abundant contact efficiency of reaction mass can be improved on the one hand, on the other hand there is good heat transfer efficiency, reaction just can be carried out at a lower temperature, avoid the coking of catalyzer and cause catalytic activity rapid deactivation, there is good prospects for commercial application.
Summary of the invention
Goal of the invention: the object of the present invention is to provide monobromethane in a kind of microchannel to prepare the synthetic method of alkene and aromatic hydrocarbons, and the recycling of the hydrogen bromide generated in reaction process, reduce the corrosion to equipment and environmental pollution, to reach the object of preparation method and the comprehensive utilization natural gas source opening up new alkene and aromatic hydrocarbons.
Technical scheme: in micro passage reaction of the present invention, the method for continuous production alkene and aromatic hydrocarbons comprises the following steps:
1) under the effect of carrier gas N2, passed into by monobromethane and be equipped with in the micro passage reaction of catalyzer, at 100-500 DEG C, catalyzed reaction is carried out;
2) reaction mixture cooling is collected, and obtains alkene and aromatic hydrocarbons;
3) hydrogen bromide that reaction generates is passed into and is equipped with in the passage of metal oxide, obtain metal bromide, then to pass into oxygen recovery be metal oxide and bromine;
4) by the metal oxide produced for step 3) in recycling, the bromine of generation stores as methane step 1) in the bromine source of monobromethane.
Further, described catalyzer is one or more in modified HZSM-5, SBA-15, MCM-41 and SAPO-5.
Further, described catalyzer is modified HZSM-5 molecular sieve, its SiO
2/ Al
2o
3than being 50-300.
Further, described modified HZSM-5 molecular sieve is that one or several in Na, K, Mg, Ca, Co, Mn, Zr, Nb, Mo, Cu, Zn, Ag, Au, Ba, Pd, Rh, Ir, Pt, Fe, Ni, Ce, P, B carry out modified product to molecular sieve HZSM-5.
Further, step 1) described in temperature of reaction at 100-400 DEG C.
Further, step 1) in monobromethane flow velocity in the microchannel that catalyzer is housed be 1-500mL/min.This flow velocity size is the flow rates not affecting reaction realization, and actual flow velocity can specifically adjust as required.
Further, described metal oxide be in Mg, Ca, Co, Zr, Ti, Cr, Mo, Al, Sn, As, Cu, Zn, Ag, Ba, Mn, Fe, Ce, P one or more.
Further, described micro passage reaction is of a size of internal diameter 1-50mm, and external diameter is 2-60mm, and length is 0.5-50m.
Further, described microreactor comprises micro-reaction tubes, inertia cooling gas tank, flow director, prolong, condensate collector, subcooling circulation device, thermopair B, insulating pipe and CH
3br vapour generator, described inertia cooling gas tank outlet is connected to flow director, the outlet effluent air of described flow director and CH
3one end of described microchannel reaction tubes is accessed after the gas and vapor permeation of the outlet outflow of Br vapour generator; The outlet effluent air of described flow director and CH
3the outlet effluent air of Br vapour generator together imports insulating pipe, and insulating pipe accesses one end of described microchannel reaction tubes again; Described CH
3br vapour generator comprises micro-injection pump, glass heats band and thermopair A, described micro-injection pump discharge is connected to described glass heats band, accesses one end of described microchannel reaction tubes after the gas and vapor permeation that the outlet effluent air of described glass heats band and the outlet of described flow director are flowed out; The other end of described microchannel reaction tubes accesses described cooling tube, and described cooling tube outlet is connected to condensate collector, and described subcooling circulation device is connected with prolong; Described thermopair B is arranged in the reaction tubes of described microchannel; Also comprise temperature regulator, described thermopair A and thermopair B is connected to described temperature regulator respectively, and described temperature regulator is connected to described flow director.
The present invention compared with prior art, its beneficial effect is: the invention provides monobromethane in a kind of microchannel and prepare the synthetic method of alkene and aromatic hydrocarbons, and the recycling of the hydrogen bromide generated in reaction process, reduce the corrosion to equipment and environmental pollution, to reach the object of preparation method and the comprehensive utilization natural gas source opening up new alkene and aromatic hydrocarbons.
Accompanying drawing explanation
Fig. 1 is the microreactor structural representation used in the present invention;
Fig. 2 is the microchannel reaction tubular construction schematic diagram used in the present invention.
Embodiment
Below technical solution of the present invention is described in detail, but protection scope of the present invention is not limited to described embodiment.
Embodiment 1:
The present invention is at carrier gas N
2effect under, passed into by monobromethane and be equipped with in the micro passage reaction of catalyzer, at 100-500 DEG C, catalyzed reaction is carried out, reaction mixture cooling collect, obtain alkene and aromatic hydrocarbons.The hydrogen bromide that reaction generates passes into and is equipped with in the passage of metal oxide, obtains metal bromide, then to pass into oxygen recovery be metal oxide and bromine, realize the cycling and reutilization of metal oxide, and the bromine generated stores the bromine source as methane monobromethane.
The catalyzer of above-mentioned monobromethane alkene and aromatic hydrocarbons is at least one in modified HZSM-5, SBA-15, MCM-41, SAPO-5.
In the method for above-mentioned monobromethane alkene and aromatic hydrocarbons, it is characterized in that, the SiO of described modified HZSM-5 molecular sieve
2/ Al
2o
3than being 50-300.
In the method for above-mentioned monobromethane alkene and aromatic hydrocarbons, it is characterized in that, described modified HZSM-5 molecular sieve is that one or several adopting in Na, K, Mg, Ca, Co, Mn, Zr, Nb, Mo, Cu, Zn, Ag, Au, Ba, Pd, Rh, Ir, Pt, Fe, Ni, Ce, P, B carry out modified product to molecular sieve HZSM-5.
In the method for above-mentioned monobromethane alkene and aromatic hydrocarbons, it is characterized in that, described temperature of reaction is at 100-400 DEG C.
In the method for above-mentioned monobromethane alkene and aromatic hydrocarbons, it is characterized in that, monobromethane flow velocity in the microchannel that catalyzer is housed is 1-500mL/min.
In the method for above-mentioned monobromethane alkene and aromatic hydrocarbons, it is characterized in that, described metal oxide is one or several in Mg, Ca, Co, Zr, Ti, Cr, Mo, Al, Sn, As, Cu, Zn, Ag, Ba, Mn, Fe, Ce, P.
In the method for above-mentioned monobromethane alkene and aromatic hydrocarbons, micro passage reaction is of a size of internal diameter 1-50mm, and external diameter is 2-60mm, and length is 0.5-50m.
One, the preparation of catalyzer
Embodiment 1
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the HZSM-5 molecular sieve that the 8g silica alumina ratio bought in Catalyst Factory, Nankai Univ is 60, at room temperature floods 6h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 2h in 120 DEG C of baking ovens first, then in retort furnace 600 DEG C of roasting 3h, obtain the catalyst A of modification after naturally cooling.
Embodiment 2
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the HZSM-5 molecular sieve that the 8g silica alumina ratio bought in Catalyst Factory, Nankai Univ is 80, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 400 DEG C of roasting 5h, obtain the catalyst B of modification after naturally cooling.
Embodiment 3
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the HZSM-5 molecular sieve that the 8g silica alumina ratio bought in Catalyst Factory, Nankai Univ is 100, at room temperature floods 10h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 8h in 120 DEG C of baking ovens first, then in retort furnace 300 DEG C of roasting 6h, obtain the catalyzer C of modification after naturally cooling.
Embodiment 4
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the HZSM-5 molecular sieve that the 8g silica alumina ratio bought in Catalyst Factory, Nankai Univ is 120, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 8h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyzer D of modification after naturally cooling.
Embodiment 5
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the HZSM-5 molecular sieve that the 8g silica alumina ratio bought in Catalyst Factory, Nankai Univ is 200, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 8h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyzer E of modification after naturally cooling.
Embodiment 6
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the HZSM-5 molecular sieve that the 8g silica alumina ratio bought in Catalyst Factory, Nankai Univ is 300, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 8h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyzer F of modification after naturally cooling.
Embodiment 7
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available SBA-15 of 8g, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyzer G of modification after naturally cooling.
Embodiment 8
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available MCM-41 of 8g, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyzer H of modification after naturally cooling.
Embodiment 9
Taking 0.6g phosphoric acid is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available SAPO-5 of 8g, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyst I of modification after naturally cooling.
Embodiment 10
Taking 0.6g nitrocalcite is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 8g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 8h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyzer J of modification after naturally cooling.
Embodiment 11
Taking 0.6g nitrocalcite is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available MCM-41 of 8g, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 8h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyzer K of modification after naturally cooling.
Embodiment 12
Taking 0.6g nitrocalcite is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available SAPO-5 of 8g, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 8h in 120 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 6h, obtain the catalyzer L of modification after naturally cooling.
Embodiment 13
Taking 0.6g cupric nitrate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 8g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 10h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 600 DEG C of roasting 6h, obtain the catalyzer M of modification after naturally cooling.
Embodiment 14
Taking 0.6g cupric nitrate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available MCM-41 of 8g, at room temperature floods 10h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 600 DEG C of roasting 6h, obtain the catalyst n of modification after naturally cooling.
Embodiment 15
Taking 0.6g cupric nitrate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available SAPO-5 of 8g, at room temperature floods 10h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 600 DEG C of roasting 6h, obtain the catalyzer O of modification after naturally cooling.
Embodiment 16
Taking 0.6g ammonium molybdate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 8g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 6h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 2h in 120 DEG C of baking ovens first, then in retort furnace 400 DEG C of roasting 6h, obtain the catalyst P of modification after naturally cooling.
Embodiment 17
Taking 0.6g ammonium molybdate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available MCM-41 of 8g, at room temperature floods 6h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 2h in 120 DEG C of baking ovens first, then in retort furnace 400 DEG C of roasting 6h, obtain the catalyzer Q of modification after naturally cooling.
Embodiment 18
Taking 0.6g ammonium molybdate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available SAPO-5 of 8g, at room temperature floods 6h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 2h in 120 DEG C of baking ovens first, then in retort furnace 400 DEG C of roasting 6h, obtain the catalyzer R of modification after naturally cooling.
Embodiment 19
Taking 0.6g Platinic chloride is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 8g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 300 DEG C of roasting 5h, obtain the catalyst S of modification after naturally cooling.
Embodiment 20
Taking 0.6g Platinic chloride is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available MCM-41 of 8g, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 300 DEG C of roasting 5h, obtain the catalyzer T of modification after naturally cooling.
Embodiment 21
Taking 0.6g Platinic chloride is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds the commercially available SAPO-5 of 8g, at room temperature floods 8h.The mixed solution flooded evaporate to dryness in the oil bath of 90 DEG C, the solid obtained is dry 5h in 120 DEG C of baking ovens first, then in retort furnace 300 DEG C of roasting 5h, obtain the catalyzer U of modification after naturally cooling.
Two, alkene and aromatic hydrocarbons are prepared in catalysis
Catalyst A-U obtained for embodiment 1-21 is carried out performance evaluation on micro passage reaction, and temperature of reaction is 300 DEG C, reaction conditions and the results are shown in Table 1.The concrete steps of reaction are:
1) at carrier gas N
2effect under, passed into by monobromethane and be equipped with in the micro passage reaction of catalyzer, at 300 DEG C, catalyzed reaction is carried out;
2) reaction mixture cooling is collected, and obtains alkene and aromatic hydrocarbons;
3) hydrogen bromide that reaction generates is passed into and is equipped with in the passage of metal oxide, obtain metal bromide, then to pass into oxygen recovery be metal oxide and bromine;
4) by the metal oxide produced for step 3) in recycling, the bromine of generation stores as methane step 1) in the bromine source of monobromethane.
Table 1 catalyst performance evaluation result
Embodiment 22
The present embodiment adopts catalyst A, performs following steps successively:
1) at carrier gas N
2effect under, passed into by monobromethane and be equipped with in the micro passage reaction of catalyzer, at 100 DEG C, catalyzed reaction is carried out;
2) reaction mixture cooling is collected, and obtain alkene and aromatic hydrocarbons, after testing, the transformation efficiency of monobromethane is 21.2%, and the selectivity of ethene, propylene, butylene, benzene, toluene is respectively 68.4%, 12.5%, 9.7%, 3.5%, 1.6%;
3) hydrogen bromide that reaction generates is passed into and is equipped with in the passage of metal oxide, obtain metal bromide, then to pass into oxygen recovery be metal oxide and bromine;
4) by the metal oxide produced for step 3) in recycling, the bromine of generation stores as methane step 1) in the bromine source of monobromethane, the regeneration yield of metal oxide is 90%, and the rate of recovery of bromine is 85%.
Embodiment 23
The present embodiment adopts catalyst A, performs following steps successively:
1) under the effect of carrier gas N2, passed into by monobromethane and be equipped with in the micro passage reaction of catalyzer, at 500 DEG C, catalyzed reaction is carried out;
2) reaction mixture cooling is collected, and obtain alkene and aromatic hydrocarbons, after testing, the transformation efficiency of monobromethane is 73.4%, and the selectivity of ethene, propylene, butylene, benzene, toluene is respectively 36.6%, 24.3%, 18.2%, 12.5%, 6.9%;
3) hydrogen bromide that reaction generates is passed into and is equipped with in the passage of metal oxide, obtain metal bromide, then to pass into oxygen recovery be metal oxide and bromine;
4) by the metal oxide produced for step 3) in recycling, the bromine of generation stores as methane step 1) in the bromine source of monobromethane.The regeneration yield of metal oxide is 86%, and the rate of recovery of bromine is 79%.
Embodiment 24
The present embodiment adopts catalyst A, performs following steps successively:
1) under the effect of carrier gas N2, passed into by monobromethane and be equipped with in the micro passage reaction of catalyzer, at 400 DEG C, catalyzed reaction is carried out;
2) reaction mixture cooling is collected, and obtain alkene and aromatic hydrocarbons, after testing, the transformation efficiency of monobromethane is 56.9%, and the selectivity of ethene, propylene, butylene, benzene, toluene is respectively 48.2%, 21.5%, 12.9%, 11.6%, 4.4%;
3) hydrogen bromide that reaction generates is passed into and is equipped with in the passage of metal oxide, obtain metal bromide, then to pass into oxygen recovery be metal oxide and bromine;
4) by the metal oxide produced for step 3) in recycling, the bromine of generation stores as methane step 1) in the bromine source of monobromethane.The regeneration yield of metal oxide is 90%, and the rate of recovery of bromine is 85%.
Three, the preparation of metal oxide
Embodiment 25
Taking 2g nitrocalcite is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 10g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 6h.The mixed solution flooded evaporate to dryness in the oil bath of 70 DEG C, the solid obtained is dry 8h in 150 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 5h, obtain load metal oxide M1 after naturally cooling.
Embodiment 26
Taking 2g zinc nitrate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 10g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 6h.The mixed solution flooded evaporate to dryness in the oil bath of 70 DEG C, the solid obtained is dry 8h in 150 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 5h, obtain load metal oxide M2 after naturally cooling.
Embodiment 27
Taking 2g cupric nitrate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 10g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 6h.The mixed solution flooded evaporate to dryness in the oil bath of 70 DEG C, the solid obtained is dry 8h in 150 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 5h, obtain load metal oxide M3 after naturally cooling.
Embodiment 28
Taking 2g manganous nitrate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 10g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 6h.The mixed solution flooded evaporate to dryness in the oil bath of 70 DEG C, the solid obtained is dry 8h in 150 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 5h, obtain load metal oxide M4 after naturally cooling.
Embodiment 29
Taking 2g iron nitrate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 10g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 6h.The mixed solution flooded evaporate to dryness in the oil bath of 70 DEG C, the solid obtained is dry 8h in 150 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 5h, obtain load metal oxide M5 after naturally cooling.
Embodiment 30
Taking 2g magnesium nitrate is dissolved in 20g deionized water, and stirred at ambient temperature 10min makes it mix, and adds 10g and buys HZSM-5 molecular sieve in Catalyst Factory, Nankai Univ, at room temperature flood 6h.The mixed solution flooded evaporate to dryness in the oil bath of 70 DEG C, the solid obtained is dry 8h in 150 DEG C of baking ovens first, then in retort furnace 500 DEG C of roasting 5h, obtain load metal oxide M6 after naturally cooling.
In the present invention's preparation, the microreactor structure of use is as shown in Figure 1,
A kind of continuous production alkene that the present embodiment provides and the microchannel reaction unit of aromatic hydrocarbons, is characterized in that adopting micro-reaction structure device, can reduce temperature of reaction greatly, control objectives product.It comprises rare gas element cooling tube 1 is N in the present embodiment
2device, CH
3br vapour generator 3 sets CH
3the input speed of Br, becomes CH after being heated by glass heats band 4
3br steam, at CH
3in Br vapour generator 3, buffering forms stable CH
3br steam, at the control N by flow director 16
2sample introduction pressure, by CH
3br passes in microchannel reaction tubes 8.In order to avoid CH
3br is cooled to liquid in course of conveying, is achieved heat insulation function by insulating pipe 6.Temperature regulator 7 controls the temperature in the microchannel reaction tubes 8 of reaction silica glass, when collecting temperature is stabilized in 300-400 degree Celsius, can react.The silica wool 9 at reaction tubes two ends is the filtering nets made in order to avoid the peeling off blocking channel of catalyzer 10.Thermopair B11, thermal insulation layer 12, heating rod 13 is combined into heating unit.React through the temperature of setting with after the residence time, the alkene generated or aromatic hydrocarbons through prolong 14 cooling of cold-40 degrees Celsius, at condensate collector 15.Subcooling circulation device 17 is for providing low-temperature receiver.
If Fig. 2 is that microchannel of the present invention reaction tubes 8 comprises body 81, the inwall of body 81 has the curing catalysts 82 of coating after fixing on inwall.
Temperature of reaction can be realized by thermometric instrument controlling box, and reaction time can by CH
3the sample introduction speed of Br, the size of microchannel silica tube internal diameter and length and N
2pressure size control.In micro-channel tubes internal diameter and length one timing, N
2pressure larger, then CH
3br is shorter by the time of reaction tubes, due to CH
3the content of Br is at N
2minute quantity is accounted for therefore, N in atmosphere
2the time flowing through reaction tubes can regard as CH
3the time that Br stops in retort.Work as N
2, CH
3certain and silica tube length one timing of the flow of Br, the internal diameter of crystal reaction tube is larger, and the residence time is shorter; Otherwise work as N
2, CH
3certain and silica tube internal diameter one timing of the flow of Br, the longer then reaction time of pipeline is longer.Comprehensive Control sample introduction speed and by the length of key part and the characteristic dimension of passage control react the residence time, and then control to target product yield and selectivity.
As mentioned above, although represented with reference to specific preferred embodiment and described the present invention, it shall not be construed as the restriction to the present invention self.Under the spirit and scope of the present invention prerequisite not departing from claims definition, various change can be made in the form and details to it.
Claims (11)
1. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction, is characterized in that, comprise the following steps:
1) at carrier gas N
2effect under, passed into by monobromethane and be equipped with in the micro passage reaction of catalyzer, at 100-500 DEG C, catalyzed reaction is carried out;
2) reaction mixture cooling is collected, and obtains alkene and aromatic hydrocarbons;
3) hydrogen bromide that reaction generates is passed into and is equipped with in the passage of metal oxide, obtain metal bromide, then to pass into oxygen recovery be metal oxide and bromine;
4) by the metal oxide produced for step 3) in recycling, the bromine of generation stores as methane step 1) in the bromine source of monobromethane.
2. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction according to claim 1, is characterized in that, described catalyzer is one or more in modified HZSM-5, SBA-15, MCM-41 and SAPO-5.
3. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction according to claim 2, it is characterized in that, described catalyzer is modified HZSM-5 molecular sieve, its SiO
2/ Al
2o
3than being 50-300.
4. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction according to claim 3, it is characterized in that, described modified HZSM-5 molecular sieve is that one or several in Na, K, Mg, Ca, Co, Mn, Zr, Nb, Mo, Cu, Zn, Ag, Au, Ba, Pd, Rh, Ir, Pt, Fe, Ni, Ce, P, B carry out modified product to molecular sieve HZSM-5.
5. modified molecular screen according to claim 3 prepares as follows:
(1) properties-correcting agent is soluble in water, dissolve completely and add molecular sieve wherein, under room temperature, flood 6 ~ 10h;
(2) in 80 DEG C of oil baths, after evaporate to dryness, get solid part dry 2 ~ 8h at 80 ~ 120 DEG C by processing the mixed system obtained in step (1), then at 300 ~ 600 DEG C roasting 3 ~ 6h, obtain modified molecular screen.
6. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction according to claim 1, is characterized in that, step 1) described in temperature of reaction be 100-400 DEG C.
7. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction according to claim 1, is characterized in that, step 1) in monobromethane flow velocity in the microchannel that catalyzer is housed be 1-500mL/min.
8. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction according to claim 1, it is characterized in that, described metal oxide be in Mg, Ca, Co, Zr, Ti, Cr, Mo, Al, Sn, As, Cu, Zn, Ag, Ba, Mn, Fe, Ce, P one or more.
9. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction according to claim 1, it is characterized in that, described micro passage reaction is of a size of internal diameter 1-50mm, and external diameter is 2-60mm, and length is 0.5-50m.
10. the method for continuous production alkene and aromatic hydrocarbons in micro passage reaction according to claim 1, it is characterized in that, described microreactor comprises micro-reaction tubes, inertia cooling gas tank (1), flow director (16), prolong (14), condensate collector (15), subcooling circulation device (17), thermopair B (11), insulating pipe (6) and CH
3br vapour generator (3), described inertia cooling gas tank (1) outlet is connected to flow director (16), the outlet effluent air of described flow director (16) and CH
3one end of described microchannel reaction tubes is accessed after the gas and vapor permeation of the outlet outflow of Br vapour generator (3); The outlet effluent air of described flow director (16) and CH
3the outlet effluent air of Br vapour generator (3) together imports insulating pipe (6), and insulating pipe (6) accesses one end of described microchannel reaction tubes again; Described CH
3br vapour generator (3) comprises micro-injection pump (2), glass heats band (4) and thermopair A (5), described micro-injection pump (2) outlet is connected to described glass heats band (4), accesses one end of described microchannel reaction tubes after the gas and vapor permeation that the outlet effluent air of described glass heats band (4) and the outlet of described flow director (16) are flowed out; The other end of described microchannel reaction tubes accesses described cooling tube (14), described cooling tube outlet is connected to condensate collector (15), and described subcooling circulation device (17) is connected with prolong (14); Described thermopair B (11) is arranged in the reaction tubes of described microchannel; Also comprise temperature regulator (7), described thermopair A (5) and thermopair B (11) are connected to described temperature regulator (7) respectively, and described temperature regulator (7) is connected to described flow director (16).
The method of continuous production alkene and aromatic hydrocarbons in 11. micro passage reactions according to claim 9, it is characterized in that, described micro-reaction tubes comprises body and curing catalysts (82), described body (81) is provided with catalytic section, described curing catalysts (82) is uniform curing on the inwall of described body (81) catalytic section, the catalytic section of described body (81) is arranged at the central authorities of described body (81), described body two ends are provided with fillter section, filtering net is provided with in the body (81) of described fillter section, the shape of described body (81) is Straight or volution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106117002A (en) * | 2016-07-07 | 2016-11-16 | 浙江大学 | A kind of method of bimetallic oxide loaded catalyst catalysis bromomethane aromatisation |
| WO2021213361A1 (en) * | 2020-04-20 | 2021-10-28 | 中国石油化工股份有限公司 | Device and method for preparing polyalphaolefin |
| CN115010651A (en) * | 2022-05-11 | 2022-09-06 | 合肥立方制药股份有限公司 | Fixed bed synthesis method of N- (4-fluorobenzylamino) -1-methylpiperidine |
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| US20090005620A1 (en) * | 2004-04-16 | 2009-01-01 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| CN102947249A (en) * | 2010-06-14 | 2013-02-27 | 马拉索恩科技有限责任公司 | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| CN104998587A (en) * | 2015-06-04 | 2015-10-28 | 南京工业大学 | Micro-channel reacting device for preparing olefin and arene continuously |
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| US20090005620A1 (en) * | 2004-04-16 | 2009-01-01 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| CN102947249A (en) * | 2010-06-14 | 2013-02-27 | 马拉索恩科技有限责任公司 | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
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| CN106117002A (en) * | 2016-07-07 | 2016-11-16 | 浙江大学 | A kind of method of bimetallic oxide loaded catalyst catalysis bromomethane aromatisation |
| CN106117002B (en) * | 2016-07-07 | 2019-05-07 | 浙江大学 | A kind of method of bimetallic oxide loaded catalyst catalysis bromomethane aromatisation |
| WO2021213361A1 (en) * | 2020-04-20 | 2021-10-28 | 中国石油化工股份有限公司 | Device and method for preparing polyalphaolefin |
| CN115010651A (en) * | 2022-05-11 | 2022-09-06 | 合肥立方制药股份有限公司 | Fixed bed synthesis method of N- (4-fluorobenzylamino) -1-methylpiperidine |
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