CN102950021A - Catalyst for synthesizing dimethyl ether from biomass synthetic gas through slurry bed reaction - Google Patents
Catalyst for synthesizing dimethyl ether from biomass synthetic gas through slurry bed reaction Download PDFInfo
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- CN102950021A CN102950021A CN2011102534245A CN201110253424A CN102950021A CN 102950021 A CN102950021 A CN 102950021A CN 2011102534245 A CN2011102534245 A CN 2011102534245A CN 201110253424 A CN201110253424 A CN 201110253424A CN 102950021 A CN102950021 A CN 102950021A
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- molecular sieve
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Abstract
The invention relates to a catalyst for synthesizing dimethyl ether from biomass synthetic gas through slurry bed reaction. The catalyst consists of a copper-based active component for synthesizing methanol from synthetic gas and a methanol dehydration active component SAPO-11 molecular sieve. Compared with dimethyl ether synthesized from synthetic gas by convectional methods, dimethyl ether synthesized from biomass synthetic gas through slurry bed reaction provided by the invention has good stability.
Description
Technical field
The present invention relates to a kind of biomass synthesis gas synthesizing dimethyl ether catalyst for slurry reactor.This catalyst comprises that the copper-based active component of synthesis gas synthesizing methanol and methanol dehydration active component SAPO-11 molecular sieve form.Synthesizing dimethyl ether by synthetic gas with routine is compared, and the present invention is used for slurry reactor biomass synthesis gas dimethyl ether synthesis, has good stability, and within the time period of operation, the catalyst reaction performance remains unchanged substantially.
Background technology
Biomass energy is as the abundant regenerative resource of reserves, and its clean utilization also helps the improvement of global environmental pollution when alleviating the fossil resource energy crisis.At present, biomass energy utilization technologies mainly is divided into two large classes, and the one, biomass conversion is power technology, the one, be high-grade fuel with biomass conversion, mainly concentrate on preparing liquid fuel and hydrogen fuel aspect.Living beings indirect liquefaction technology refers to living beings at first are converted into synthesis gas, and then the synthol ether fuel.
Dimethyl ether is a kind of important chemical intermediate, and mainly as aerosol, propellant and cold-producing medium etc., but as the cleaning liquid fluid fuel, its application prospect is more extensive, once is described as " 21 century fuel ".At present, process for synthesis of dimethyl ether mainly contains two, and the one, synthesis gas is the synthesizing methanol generation dimethyl ether that dewaters again at first, and the one, synthesis gas passes through composite catalyst one-step synthesis dimethyl ether.The latter is owing to adopted complex catalyst system, make synthesis gas behind methanol on the catalst for synthesis of methanol, generate dimethyl ether in the dehydration component dehydration immediately, broken through the thermodynamics equilibrium limit of synthesizing methanol, the conversion ratio of CO obviously raises, and this process is not subjected to the methanol prices influence of fluctuations.Therefore synthesis gas directly synthesizes DME has become a synthetic main development direction of present DME.
Direct synthesis of dimethyl ether from synthesis gas is developed rapidly at recent two decades, and people have carried out a large amount of R and D to its catalyst and technique.But up to the present, still have two large problems to limit further developing of this technology, i.e. the heat-obtaining problem of course of reaction and the stability problem of catalyst.How to solve these two problems and become these field scientific circles and the common focus of paying close attention to of industrial quarters.
The synthesis gas that the synthetic patent documentation of present dimethyl ether adopts mostly concentrates on the synthesis gas that pure synthesis gas, coal based synthetic gas, natural gas base synthesis gas etc. derive from conventional method.Reported the copper base SO of pure synthesizing dimethyl ether by synthetic gas in the fixed bed reactors such as CN1657163A
4 2-Modification γ-Al
2O
3Bifunctional catalyst; CN1883804A has reported by CuO-ZnO-Al
2O
3/ HZSM-5 and CuO-ZnO-ZrO
2The synthesis gas preparing dimethy ether composite catalyst that/HZSM-5 forms has not only improved the CO conversion ratio, and has reduced accessory substance CO
2Content.CN1730451A has reported the C301 catalst for synthesis of methanol of coal based synthetic gas dimethyl ether synthesis slurry reactor and the Al of MnO-ZnO modification
2O
3The composite catalyst that forms, but do not report the stability of its catalytic reaction.CN1172893C has then reported a kind of integrated technology process by direct synthesis of dimethyl ether from synthesis gas, being characterized as of this technique: take synthesis gas as raw material by the two-stage reaction dimethyl ether synthesis; First paragraph reaction is to be dimethyl ether with the synthesis gas Partial Conversion in paste state bed reactor; Second segment reaction is in the fixed bed reactors behind paste state bed reactor remaining synthesis gas to be further converted to dimethyl ether.Because the liquid phase medium that this invention is added in paste state bed reactor has larger thermal capacitance and good heat transfer property, therefore can substantially realize isothermal operation and synthesising reacting heat is in time shifted out.Strengthen in the remaining synthesis gas conversion process at the fixed bed reactors that are right after, because most of synthesis gas has been converted into dimethyl ether in paste state bed reactor, only have the small part synthesis gas to transform, therefore will avoid beds temperature runaway sintered catalyst.This integrated technique can finally obtain high CO conversion ratio in addition, has omitted the synthesis gas recycle compressor, and has saved the circulation work done during compression.This integrated technique requires slurry attitude bed catalyst that good stability is arranged.
This patent research emphasis is to adopt the synthesis gas (abbreviation biomass synthesis gas) that derives from living beings, compare with traditional synthesis gas, the hydrogen-carbon ratio of biomass synthesis gas is lower, the foreign gas such as nitrogen, carbon dioxide, methane that contains high level, thereby adopt its dimethyl ether synthesizing reaction more complicated, harsher to the catalyst requirement, simultaneously the present invention more is applicable to the slurry reactor system.
Summary of the invention
The objective of the invention is to contain for biomass synthesis gas the characteristics of the foreign gases such as high-load nitrogen, carbon dioxide and methane, the characteristics of synthesizing dimethyl ether by synthetic gas slurry reactor, a kind of catalyst of suitable biomass synthesis gas dimethyl ether synthesis slurry reactor is provided.
The present invention adopts following method to realize:
Catalyst system therefor is comprised of methanol synthesis catalyst and SAPO molecular sieve. the commercial catalyst for synthesizing copper based methanol (abbreviation catalyst for methanol) that methanol synthesis catalyst is produced from Shenyang Catalyst Plant, 200 ℃ of preliminary treatment 2 hours in air before using; SAPO molecular sieve, HZSM-5 molecular sieve be from Kai Meisite Science and Technology Ltd., 500 ℃ of preliminary treatment 4 hours in air before using.Catalyst for methanol and SAPO molecular sieve mix by a certain percentage, grinding, compressing tablet, to be sized to certain granules for subsequent use.For comparing, prepared conventional Cu-ZnO-Al
2O
3/ HZSM-5 synthesis gas preparing dimethy ether composite catalyst, and estimate its biomass synthesis gas dimethyl ether synthesis catalytic perfomance.Implementation method is further specified by following embodiment in detail, but is not limited to following embodiment.
Catalyst for synthesizing copper based methanol (abbreviation catalyst for methanol) also can adopt the coprecipitation self-control, but reference literature (Qingj ie Ge, Youmei Huang, Fengyan Qiu, Shuben Li, AppliedCatalysis A, 1998:23-30) preparation.
Catalyst of the present invention is comprised of synthesis gas synthetic copper methoxide base active component and methanol dehydration active component SAPO molecular sieve.Synthesizing dimethyl ether by synthetic gas catalyst with routine is compared, and the present invention is used for slurry reactor biomass synthesis gas dimethyl ether synthesis, has good stability.
Description of drawings
Fig. 1. the biomass synthesis gas reaction of preparing dimethyl ether performance of catalyst E;
Fig. 2. reaction temperature is on the impact of synthesis of dimethyl ether with synthesis gas one-step;
Fig. 3. reaction pressure is on the impact of synthesis of dimethyl ether with synthesis gas one-step;
Fig. 4. the reaction stability test of catalyst A.
The specific embodiment
Embodiment 1
Take by weighing the pretreated catalyst for methanol of 9 grams and 3 and restrain pretreated SAPO-11 molecular sieve and mix, be ground to below 100 orders, compressing tablet, moulding is crushed to the 40-60 order, obtains catalyst A.
Take by weighing 8 gram catalyst for methanol and 2 and restrain the SAPO-11 molecular sieves and mix, be ground to below 100 orders, compressing tablet, moulding is crushed to the 20-40 order, obtains catalyst B.
Take by weighing the 10g catalyst for methanol and 2g SAPO-11 molecular sieve mixes, be ground to below 100 orders, compressing tablet, moulding is crushed to the 20-40 order, obtains catalyst C.
Take by weighing 9g catalyst for methanol and 3g γ-Al
2O
3SAPO-11 molecular sieve (SAPO-11/ γ-the Al that adds
2O
3Mass ratio=3) mix, be ground to below 100 orders, compressing tablet, moulding is crushed to the 20-40 order, obtains catalyst D.
The comparative example 1:
Take by weighing the pretreated catalyst for methanol of 9 grams and 3 and restrain pretreated HZSM-5 molecular sieve and mix, be ground to below 100 orders, compressing tablet, moulding is crushed to the 40-60 order, obtains catalyst E.
The comparative example 2
Take by weighing the pretreated catalyst for methanol of 10 grams and 2 and restrain pretreated HZSM-5 molecular sieve and mix, be ground to below 100 orders, compressing tablet, moulding is crushed to the 40-60 order, obtains catalyst F.
Catalyst performance evaluation
It is the autoclave of 0.1L that paste state bed reactor adopts volume.Add composite catalyst 5 grams to be measured in reactor, inertia liquid phase heat carrier (atoleine) is 60ml.Reducing gases (pure H
2) air speed is 1000h, reduction temperature is 250 ℃, the recovery time is 12h.After reduction finished, (percent by volume consisted of: 33.3%CO, 43.2%H to switch unstripped gas
2, 10.3%CO
2, 2.9%CH
4, 10.4%N
2) under corresponding condition, react.The product of reaction keeps carrying out more than 120 ℃ on-line analysis.Adopt Japanese Shimadzu GC-8A gas chromatograph, TDX-01 chromatogram column analysis N
2, CO, CH
4And CO
2, column length 1.5m detects with thermal conductivity detector (TCD); GDX-401 chromatogram column analysis methyl alcohol, dimethyl ether and hydro carbons, column length 1.5m detects with hydrogen flame ionization detector.Adopt the synthetic front and back of dimethyl ether carbon/nitrogen than constant, and Carbon balance is calculated CO conversion ratio and selectivity of product.
The contrast experiment 1
At 240 ℃, 4.0MPa, 1000h
-1Under the condition, tested the reactivity worth of catalyst E, the result is as shown in Figure 1. as seen from Figure 1, under above-mentioned reaction condition, the biogas reaction of preparing dimethyl ether poor-performing of B catalyst in the paste state bed reactor, reaction near the 35h scope in, the CO conversion ratio only has 26%, although DME, is dropped rapidly to below 80% in 35 hours of reaction more than 90% at the selective initial value of organic products.This shows that in the paste state bed reactor system E composite catalyst also is not suitable for the biomass synthesis gas dimethyl ether synthesizing reaction.
Experiment 1
In paste state bed reactor, the biomass synthesis gas dimethyl ether synthesizing reaction performance of catalyst C and F is listed in table 1, and reaction condition is: 250 ℃, and 5MPa, air speed is 1000h
-1As seen from Table 1: catalyst F can't satisfy biomass synthesis gas dimethyl ether synthesis slurry reactor to the requirement of dehydration component, and secondary response product hydro carbons is more in the product, so that selectively on the low side at organic products of DME.Comparatively speaking, composite catalyst C of the present invention and D have not only shown suitable CO conversion ratio, and the selective obviously increase of dimethyl ether, and the growing amount of byproduct hydrocarbon is obviously less, and this is less relevant with its surperficial dimethyl ether generation deep dehydration.According to the characteristics of slurry reactor, the water that reaction generates can not in time be diffused in catalyst the slurries of reactor, therefore reduces the stability that the deep dehydration reaction will be conducive to catalyst.
In the composite catalyst two component ratios on reactivity worth impact in slurry reactor because that the existence of liquid inert medium becomes is obvious, the particularly impact of conversion ratio, embody both ways: the one, catalyst for methanol/molecular sieve ratio is hour, hydrogenation component is less, be unfavorable for that CO transforms, but dehydration component is conducive to the converted in-situ of intermediate product more, and then is conducive to the raising of CO conversion ratio; The one, catalyst for methanol/when molecular sieve ratio was larger, hydrogenation component was many, be conducive to CO and transform, but the less converted in-situ of intermediate product that is unfavorable for of dehydration component removes, and was unfavorable for that the CO conversion ratio improves.Therefore, the variation of active component is comparatively complicated to catalysts influence, and it then is the general performance of the above-mentioned various factors of active component ratio that the reactivity worth of catalyst changes.Table 2 has been listed 250 ℃, 5MPa, air speed and has been respectively 500h
-1And 1000h
-1The impact of composite catalyst A, the B under the reaction condition, C preparing dimethylether from synthetic gas by reaction performance.Can find out that from table the performance of catalyst A is comparatively balanced, be with the obvious advantage under the condition of 500h-1 in air speed particularly.Therefore think the Cu-ZnO-Al of slurry reactor of biomass synthesis gas dimethyl ether synthesis
2O
3/ SAPO-11 composite catalyst active component ratio is 3: 1 o'clock the bests.
At 5.0MPa, 500h
-1Condition under investigated the impact of reaction temperature on catalyst C reactivity worth, experimental result is shown in Fig. 2.As can be seen from Figure, raise with temperature, the CO conversion ratio of reaction raises, the selective increase of product D ME, and increase trend is obvious between 240-250 ℃, and afterwards increase trend slows down.This is because temperature is excessively low, and the dehydration component of catalyst is difficult for its dehydrating function of performance in the slurry attitude bed, increases the cause that its dewatering increases gradually with temperature, this can by methyl alcohol in the product optionally variation tendency find out.In addition, excess Temperature, product DME is easy to secondary response occurs and reduces selectivity of product, and high temperature also is unfavorable for the heat endurance of copper-based catalysts in addition.
At 250 ℃, 500h
-1Investigated the pressure of slurry reactor system under the condition to the impact of catalyst C reactivity worth, the result as shown in Figure 3, as seen from the figure, increase with reaction system pressure, the CO conversion ratio continues to raise, and dimethyl ether selectively increases slightly at organic products, substantially tends towards stability behind 4.0MPa.In the preparing dimethylether from synthetic gas by reaction on slurry-state bed system, rising pressure is conducive to balance to carry out to the direction that generates dimethyl ether, and improves the conversion ratio of reaction.Consider that hypertonia can increase the compression power consumption of system, therefore for the reaction of pulpous bed dimethyl ether synthesizing, reaction pressure is difficult for too high, and 4.0-5.0MPa should be suitable pressure operation scope.
Experiment 5
Table 3 has provided 250 ℃, and the unstripped gas air speed is on the impact of catalyst C reactivity worth under the 5MPa, and experimental result is as shown in table 3.As shown in Table 3, increase with the unstripped gas air speed, the CO conversion ratio of reaction reduces gradually, and the selective variation of dimethyl ether is not obvious, and the DME space-time yield progressively is increased in 1500h
-1The time reach maximum, then progressively descend.Air speed increases, and reduce the time of contact of unstripped gas and catalyst, and the CO conversion ratio reduces, but the treating capacity of unstripped gas increases in the unit interval, so the DME space-time yield has a maximum.Consider 1500h from the space-time yield of DME
-1It should be best unstripped gas air speed.
Experiment 6
250 ℃, 5.0MPa, 500h
-1Under the condition, the reaction stability of the biomass synthesis gas dimethyl ether synthesis of catalyst A the results are shown in Fig. 4.As can be seen from Figure, catalyst A has shown good stability, and substantially without significant change, the CO conversion ratio remains on more than 40% reactivity worth, DME selectively remaining on about 97% in organic product within the time of operation.
The reactivity worth of table 1. composite catalyst C and F
Table 2 different component ratio is to the catalyst reaction performance impact
Table 3. unstripped gas air speed is on the impact of catalyst reaction performance
Claims (6)
1. biomass synthesis gas synthesizing dimethyl ether catalyst that is used for slurry reactor, it is characterized in that: described catalyst is comprised of methanol dehydration component S APO molecular sieve and catalyst for synthesizing copper based methanol, and wherein the part by weight of catalyst for synthesizing copper based methanol and SAPO molecular sieve is 1: 3-8: 1.
2. according to the described catalyst of claim 1, it is characterized in that: described methanol dehydration component S APO molecular sieve refers to the SAPO molecular sieve, or modification SAPO-11 molecular sieve, or SAPO and ZSM-5, MCM-41, Y, β, Modernite, SiO
2, Al
2O
3In one or two or more kinds composite molecular screen, wherein the doping of SAPO in composite molecular screen is 0.1-50wt%.
3. according to the described catalyst of claim 1, it is characterized in that: described modification SAPO-11 molecular sieve refers to M-SAPO-11, and M is metal oxide, and wherein the doping of M is 0.01-10wt%; The M metal oxide refers to PdO, CuO, ZnO, CaO, V
2O
5, Al
2O
3, SiO
2In one or two or more kinds.
4. according to the described catalyst of claim 1, it is characterized in that: described catalyst is used for containing the synthesis gas slurry reactor dimethyl ether synthesis of nitrogen, methane and carbon dioxide; The synthesis gas volume forms 15-50%CO, 15-50%H
2, 1-15%CO
2, 0.1-10%CH
4, 0.5-20%N
2, other gas of 0.5-5%.
5. according to the described catalyst of claim 4, it is characterized in that: other gas is other foreign gas, is Ar and/or H
2O.
6. according to claim 1 or 4 described catalyst, it is characterized in that: described synthesis gas refers to derive from the synthesis gas of living beings.
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Cited By (1)
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|---|---|---|---|---|
| CN111491732A (en) * | 2017-12-20 | 2020-08-04 | 巴斯夫欧洲公司 | Catalyst system and process for the production of dimethyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391226A (en) * | 2008-10-30 | 2009-03-25 | 上海应用技术学院 | One-step catalyst for directly preparing dimethyl ether using carbon dioxide and use method thereof |
| CN102029185A (en) * | 2010-11-26 | 2011-04-27 | 南开大学 | Catalyst for preparing dimethyl ether through methanol dehydration as well as preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391226A (en) * | 2008-10-30 | 2009-03-25 | 上海应用技术学院 | One-step catalyst for directly preparing dimethyl ether using carbon dioxide and use method thereof |
| CN102029185A (en) * | 2010-11-26 | 2011-04-27 | 南开大学 | Catalyst for preparing dimethyl ether through methanol dehydration as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JI-HYUN KIM ET AL.: "DME synthesis from synthesis gas on the admixed catalysts of Cu/ZnO/Al2O3 and ZSM-5", 《APPLIED CATALYSIS A: GENERAL》 * |
| KYE SANG YOO ET AL.: "Influence of solid acid catalyst on DME production directly from synthesis gas over the admixed catalyst of Cu/ZnO/Al2O3 and various SAPO catalysts", 《APPLIED CATALYSIS A: GENERAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111491732A (en) * | 2017-12-20 | 2020-08-04 | 巴斯夫欧洲公司 | Catalyst system and process for the production of dimethyl ether |
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