CN105148912A - Preparation method of catalyst for preparing DME (dimethyl ether) from synthesis gas with one-step method - Google Patents
Preparation method of catalyst for preparing DME (dimethyl ether) from synthesis gas with one-step method Download PDFInfo
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- CN105148912A CN105148912A CN201510479407.1A CN201510479407A CN105148912A CN 105148912 A CN105148912 A CN 105148912A CN 201510479407 A CN201510479407 A CN 201510479407A CN 105148912 A CN105148912 A CN 105148912A
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Abstract
The invention discloses a preparation method of a catalyst for preparing DME (dimethyl ether) from synthesis gas with a one-step method. The catalyst has a crystal structure of CuAl2O4 spinel and comprises Cu serving as a methanol synthesis active component and Al2O3 serving as a methanol dehydration active component, other auxiliary agents are not added, Cu is uniformly distributed in a Al2O3 framework structure, the mole ratio of Cu to Al is 1:(3-9), and the DME catalyst is prepared by calcining an aqueous solution of soluble copper salt containing organic fuel urea or citric acid and soluble aluminum salt. The prepared catalyst has good reaction activity and stability and is used for a process for preparing DME from synthesis gas with a one-step method, the CO (carbonic oxide) conversion rate is higher than 42%, and the DME selectivity is higher than 60%.
Description
Technical field
The present invention relates to a kind of preparation method of preparation of dimethyl ether from synthesis gas catalyst, particularly relate to a kind of preparation of dimethyl ether from synthesis gas method for preparing catalyst based on solution combustion method.
Background technology
One-step method from syngas direct preparation of dimethyl ether (DME) passes in synthesis reactor mainly containing CO and H
2synthesis gas, complete in reactor simultaneously methyl alcohol synthesis and dehydration two courses of reaction, directly to prepare dimethyl ether.One-step method from syngas direct preparation of dimethyl ether mainly adopts bifunctional catalyst, namely contains the composite catalyst of methanol synthesis catalyst and methanol dehydration catalyst simultaneously.The preparation method of current bifunctional catalyst mainly contains mixing method, coprecipitation, Slurry mixing, infusion process, co-precipitation, precipitation of joint sedimentation, sol-gal process etc.
In bifunctional catalyst, the activity of methanol synthesis catalyst directly affects the reactivity of one-step method from syngas preparation of dimethyl ether.At present a kind of common recognition is existed for the methanol-fueled CLC active component in composite catalyst, no matter be namely the methanol synthesis catalyst of copper base or chromium base, all need to add zinc as auxiliary agent, to improve activity and the stability of catalyst.Meanwhile, in order to improve the reactivity of composite catalyst, by adding other auxiliary agents, modification can also be carried out to methanol synthesis catalyst.CN1413767A, CN101402042A, CN1883798A, CN1233527A, CN101157049A etc. adopt the elements such as Zr, Mg, Fe, Mn, B, Ce or La to carry out modification to catalyst respectively, thus improve the Activity and stabill of composite catalyst in the reaction of one-step method from syngas preparation of dimethyl ether.But the preparation technology of above-mentioned composite catalyst is often comparatively complicated, and technological parameter condition is harsh, and can produce a large amount of contaminated wastewater environment when Kaolinite Preparation of Catalyst.
Jiang etc. (MicroporousandMesoporousMaterials, 2012,164,3-8) report a kind of central hole structure Catalysts Cu/γ-Al adopting solvent volatilization self-assembly method to prepare
2o
3, and be applied in the reaction of one-step method from syngas preparation of dimethyl ether, under 5MPa, 310 DEG C of conditions, its CO conversion ratio and DEM is selective reaches 72% and 69% respectively.Above-mentioned result of study shows, Zn is not the necessary composition of methanol synthesis catalyst, when not adding other auxiliary agents, only have Cu still can have higher reactivity in the reaction of one-step method from syngas preparation of dimethyl ether as the methanol synthesis catalyst of active component.
Summary of the invention
The object of this invention is to provide a kind of preparation method of one-step method from syngas preparation of dimethyl ether catalyst, in the reaction of one-step method from syngas preparation of dimethyl ether, there is higher CO conversion ratio and DME optionally catalyst to prepare one.
One-step method from syngas preparation of dimethyl ether catalyst of the present invention has CuAl
2o
4spinel crystal structure, by as the Cu of methanol-fueled CLC active component and the Al as methanol dehydration active component
2o
3composition, do not add other auxiliary agents, Cu is evenly distributed on Al
2o
3in skeleton structure, the mol ratio of Cu and Al is 1: 3 ~ 9.
The feature of one-step method from syngas preparation of dimethyl ether catalyst of the present invention does not add other any auxiliary agents comprising Zn element that catalyst for methanol commonly uses etc., and Cu is evenly distributed on Al simultaneously
2o
3in skeleton structure, form CuAl
2o
4spinel crystal structure.
The preparation method of catalyst of the present invention is: account for the ratio of Cu+Al mole of total amount 10 ~ 25% according to Cu mole in catalyst, soluble copper salt and aluminum soluble salt are dissolved in water, interpolation organic-fuel urea or citric acid obtain solution, and under air atmosphere, described in 600 ~ 800 DEG C of roastings, solution prepares catalyst.
Wherein, when taking urea as fuel, the mol ratio of Cu+Al mole of total amount and urea is 1: 2 ~ 2.5, and when taking citric acid as fuel, the mol ratio of Cu+Al mole of total amount and citric acid is 1: 0.75 ~ 1.
Wherein, described soluble copper salt and aluminum soluble salt can be respective nitrate, sulfate, chlorate, acetate etc., and the present invention is preferably nitrate.
In preparation method of the present invention, preferably, be described solution is warming up to 600 ~ 800 DEG C with the heating rate of 3 ~ 5 DEG C/min carry out roasting.
Further, roasting time of the present invention is preferably 2 hours.
The catalyst prepared by said method of the present invention is for the synthesis of in gas one-step method preparation of dimethyl ether technique, and the conversion ratio of CO reaches more than 42%, the highest can reach 56.3%, DME selective more than 60%, the highlyest can reach 66.1%.
Because the Cu in catalyst of the present invention is evenly distributed on Al
2o
3in skeleton structure, therefore, the activity that catalyst is excellent is imparted.First, the Cu as methanol-fueled CLC active component is dispersed in integer catalyzer with the decentralization of atom level, improves the utilization rate of methanol synthesis catalyst and the decentralization of Cu.Secondly, the activated centre that Cu reacts as methanol-fueled CLC, is embedded in Dehydration of methanol active component A l
2o
3skeleton structure in, the methyl alcohol generated in Cu activated centre can Al in its vicinity
2o
3middle rapid dehydration generates dimethyl ether, shortens reaction distance, makes catalyst have higher reactivity.Again, Cu activated centre is embedded in Al
2o
3structure in skeleton structure, it also avoid Cu and sinters in course of reaction or assemble and cause catalyst activity to reduce even inactivation, make catalyst have excellent stability.Therefore, although do not add Zn conventional in methanol synthesis catalyst as auxiliary agent in catalyst of the present invention, the catalyst of preparation still has higher reactivity and stability.
The present invention with the soluble copper salt of cheapness, aluminum soluble salt, citric acid or urea for raw materials, directly raw material dissolving is mixed rear roasting and make catalyst, greatly simplify the preparation process of catalyst, the zero-emission of waste water is achieved in preparation process, provide a kind of green, inexpensive, easy one-step method from syngas prepares the preparation method of dimethyl ether catalyst, and in catalyst, the utilization rate of metallic atom is 100%.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photograph and the distribution diagram of element that embodiment 1 prepares catalyst.
Fig. 2 is the XRD spectra of embodiment 3 and embodiment 4 catalyst.
Fig. 3 is the TEM photo of embodiment 3 catalyst.
Detailed description of the invention
Embodiment 1
Take 0.97g nitrate trihydrate copper and 13.51g nine water aluminum nitrate, be dissolved in 10mL distilled water, add 4.8g urea, be stirred to and dissolve completely.Solution is placed in Muffle furnace, in air atmosphere, with the ramp to 600 DEG C of 3 DEG C/min, roasting 2 hours.Make 20 ~ 40 object particles after catalyst grinding roasting obtained, obtain one-step method from syngas preparation of dimethyl ether catalyst Cat-1.
Fig. 1 is ESEM and the distribution diagram of element of the catalyst using HITACHIS-4800 ESEM to obtain.As can be seen from the figure, the main component of the catalyst prepared is Cu and Al, and Cu element is in the catalyst dispersed.
The reactivity of high pressure fixed-bed micro-reactor to the present embodiment Kaolinite Preparation of Catalyst is utilized to test.Catalyst amount 1g, first by catalyst 50mL/min reducing gases (5%H before reaction
2+ 95%N
2) at 280 DEG C of reduction 4h, be cooled to catalytic reaction temperature 260 DEG C, reaction pressure 5MPa, with air speed 1500h
-1pass into and consist of H
2: the unstripped gas of CO=2: 1, carries out the reaction of one-step method from syngas preparation of dimethyl ether.After 6h is carried out in reaction, with Shimadzu GC-2014C chromatograph, on-line analysis is carried out to product.Chromatograph is equipped with two chromatographic column TCD detector, and wherein TDX-01 chromatographic column detects CO and CO
2, GDX-501 chromatographic column detects methyl alcohol, DME and hydrocarbon.Reaction pipeline is all heated to 100 DEG C with heating tape, to avoid product condensation in pipeline.Meanwhile, by industrial γ-Al
2o
3with industrial methanol synthetic catalyst C302 according to 10: 1 quality than mechanical mixture, obtain comparison catalyst sample C302/ γ-Al
2o
3, carry out catalyst reaction active testing according to the above-mentioned condition of the present embodiment.Concrete test comparison result is in table 1.
As can be seen from Table 1, the present embodiment catalyst Cat-1 has than C302/ γ-Al
2o
3the CO conversion ratio that mixed catalyst is higher and DME selective.
Embodiment 2
Take 0.97g nitrate trihydrate copper and 13.51g nine water aluminum nitrate, be dissolved in 10mL distilled water, add 5.51g urea, be stirred to and dissolve completely.Solution is placed in Muffle furnace, in air atmosphere, with the ramp to 800 DEG C of 5 DEG C/min, roasting 2 hours.Make 20 ~ 40 object particles after catalyst grinding roasting obtained, obtain one-step method from syngas preparation of dimethyl ether catalyst Cat-2.
Evaluating catalyst condition is with embodiment 1, and gained catalytic result is in table 2.
Embodiment 3
Take 1.45g nitrate trihydrate copper and 12.75g nine water aluminum nitrate, be dissolved in 10mL distilled water, add 6g urea, be stirred to and dissolve completely.Solution is placed in Muffle furnace, in air atmosphere, with the ramp to 800 DEG C of 3 DEG C/min, roasting 2 hours.Make 20 ~ 40 object particles after catalyst grinding roasting obtained, obtain one-step method from syngas preparation of dimethyl ether catalyst Cat-3.
Evaluating catalyst condition is with embodiment 1, and gained catalytic result is in table 2.
Embodiment 4
Take 1.93g nitrate trihydrate copper and 12g nine water aluminum nitrate, be dissolved in 10mL distilled water, add 6g urea, be stirred to and dissolve completely.Solution is placed in Muffle furnace, in air atmosphere, with the ramp to 800 DEG C of 5 DEG C/min, roasting 2 hours.Make 20 ~ 40 object particles after catalyst grinding roasting obtained, obtain one-step method from syngas preparation of dimethyl ether catalyst Cat-4.
Fig. 2 gives the X-ray diffraction spectrogram of catalyst Cat-3 and Cat-4, can see there is CuAl from XRD spectra
2o
4spinel crystal structure characteristic diffraction peak, do not observe CuO and Al simultaneously
2o
3characteristic diffraction peak, show the gathering not having Cu in catalyst, Cu is evenly embedded into Al
2o
3skeleton structure in, define CuAl
2o
4spinel crystal structure.And then, in the transmission electron microscope picture of the Cat-3 provided at Fig. 3, do not observe obvious CuO particle yet, show being dispersed in really in whole catalyst of Cu.Meanwhile, can also see that catalyst has the ordered mesoporous pore passage structure of about 5nm by Fig. 3.
Evaluating catalyst condition is with embodiment 1, and gained catalytic result is in table 2.
Embodiment 5
Take 2.42g nitrate trihydrate copper and 11.25g nine water aluminum nitrate, be dissolved in 10mL distilled water, add 6g urea, be stirred to and dissolve completely.Solution is placed in Muffle furnace, in air atmosphere, with the ramp to 600 DEG C of 3 DEG C/min, roasting 2 hours.Make 20 ~ 40 object particles after catalyst grinding roasting obtained, obtain one-step method from syngas preparation of dimethyl ether catalyst Cat-5.
Evaluating catalyst condition is with embodiment 1, and gained catalytic result is in table 2.
Embodiment 6
Take 0.97g nitrate trihydrate copper and 13.51g nine water aluminum nitrate, be dissolved in 10mL distilled water, add 5.76g citric acid, be stirred to and dissolve completely.Solution is placed in Muffle furnace, in air atmosphere, with the ramp to 800 DEG C of 3 DEG C/min, roasting 2 hours.Make 20 ~ 40 object particles after catalyst grinding roasting obtained, obtain one-step method from syngas preparation of dimethyl ether catalyst Cat-6.
Evaluating catalyst condition is with embodiment 1, and gained catalytic result is in table 2.
Embodiment 7
Take 1.45g nitrate trihydrate copper and 12.75g nine water aluminum nitrate, be dissolved in 10mL distilled water, add 6.65g citric acid, be stirred to and dissolve completely.Solution is placed in Muffle furnace, in air atmosphere, with the ramp to 600 DEG C of 3 DEG C/min, roasting 2 hours.Make 20 ~ 40 object particles after catalyst grinding roasting obtained, obtain one-step method from syngas preparation of dimethyl ether catalyst Cat-7.
Evaluating catalyst condition is with embodiment 1, and gained catalytic result is in table 2.
Embodiment 8
Take 2.42g nitrate trihydrate copper and 11.25g nine water aluminum nitrate, be dissolved in 10mL distilled water, add 7.68g citric acid, be stirred to and dissolve completely.Solution is placed in Muffle furnace, in air atmosphere, with the ramp to 800 DEG C of 5 DEG C/min, roasting 2 hours.Make 20 ~ 40 object particles after catalyst grinding roasting obtained, obtain one-step method from syngas preparation of dimethyl ether catalyst Cat-8.
Evaluating catalyst condition is with embodiment 1, and gained catalytic result is in table 2.
Claims (8)
1. an one-step method from syngas preparation of dimethyl ether catalyst, has CuAl
2o
4spinel crystal structure, by as the Cu of methanol-fueled CLC active component and the Al as methanol dehydration active component
2o
3composition, do not add other auxiliary agents, Cu is evenly distributed on Al
2o
3in skeleton structure, the mol ratio of Cu and Al is 1: 3 ~ 9, obtains by adding organic-fuel urea or the soluble copper salt of citric acid and the aqueous solution roasting of aluminum soluble salt.
2. the preparation method of one-step method from syngas preparation of dimethyl ether catalyst described in claim 1, account for the ratio of Cu+Al mole of total amount 10 ~ 25% according to Cu mole in catalyst, soluble copper salt and aluminum soluble salt are dissolved in water, interpolation organic-fuel urea or citric acid obtain solution, and under air atmosphere, described in 600 ~ 800 DEG C of roastings, solution prepares catalyst.
3. preparation method according to claim 2, is characterized in that the mol ratio of described Cu+Al mole total amount and urea is 1: 2 ~ 2.5.
4. preparation method according to claim 2, is characterized in that the mol ratio of described Cu+Al mole total amount and citric acid is 1: 0.75 ~ 1.
5. preparation method according to claim 2, is characterized in that described soluble copper salt and aluminum soluble salt are the one in respective nitrate, sulfate, chlorate or acetate.
6. preparation method according to claim 2, is characterized in that described soluble copper salt and aluminum soluble salt are respective nitrate.
7. preparation method according to claim 2, is characterized in that described solution is warming up to 600 ~ 800 DEG C with the heating rate of 3 ~ 5 DEG C/min carries out roasting.
8. preparation method according to claim 2, is characterized in that described roasting time is 2 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017209705A3 (en) * | 2016-05-31 | 2017-12-28 | Ptt Global Chemical Public Company Limited | Copper aluminium oxide catalyst for preparing furfuryl alcohol from furfural and a preparation of said catalyst |
| WO2019218490A1 (en) * | 2018-05-17 | 2019-11-21 | 中国科学院大连化学物理研究所 | Method for directly preparing dimethyl ether by synthesis gas |
| CN111744488A (en) * | 2020-07-01 | 2020-10-09 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
| CN112479703A (en) * | 2020-11-20 | 2021-03-12 | 辽宁石油化工大学 | Spinel solid solution material and preparation method and application thereof |
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| US4423155A (en) * | 1981-02-20 | 1983-12-27 | Mobil Oil Corporation | Dimethyl ether synthesis catalyst |
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| HEQIANG JIANG, ET AL: "One-pot synthesis of mesoporous Cu-γ-Al2O3 as bofunctional catalyst for direct dimethyl ether synthesis", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017209705A3 (en) * | 2016-05-31 | 2017-12-28 | Ptt Global Chemical Public Company Limited | Copper aluminium oxide catalyst for preparing furfuryl alcohol from furfural and a preparation of said catalyst |
| US11253841B2 (en) | 2016-05-31 | 2022-02-22 | Ptt Global Chemical Public Company Limited | Copper aluminium oxide catalyst for preparing furfuryl alcohol from furfural and a preparation of said catalyst |
| WO2019218490A1 (en) * | 2018-05-17 | 2019-11-21 | 中国科学院大连化学物理研究所 | Method for directly preparing dimethyl ether by synthesis gas |
| US11247959B2 (en) | 2018-05-17 | 2022-02-15 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for directly preparing dimethyl ether by synthesis gas |
| CN111744488A (en) * | 2020-07-01 | 2020-10-09 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
| CN111744488B (en) * | 2020-07-01 | 2022-04-19 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
| CN112479703A (en) * | 2020-11-20 | 2021-03-12 | 辽宁石油化工大学 | Spinel solid solution material and preparation method and application thereof |
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