CN1836778A - Metal modified HZSM-5 molecular screen catalyst and its preparation method and uses in preparing methyl formate - Google Patents

Metal modified HZSM-5 molecular screen catalyst and its preparation method and uses in preparing methyl formate Download PDF

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CN1836778A
CN1836778A CN 200610035278 CN200610035278A CN1836778A CN 1836778 A CN1836778 A CN 1836778A CN 200610035278 CN200610035278 CN 200610035278 CN 200610035278 A CN200610035278 A CN 200610035278A CN 1836778 A CN1836778 A CN 1836778A
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molecular sieve
metal
catalyst
hzsm
sieve catalyst
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余林
向杰
吕逵弟
孙明
郝志峰
余倩
李永峰
彭兰乔
王雪涛
许洁瑜
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Guangdong University of Technology
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Guangdong University of Technology
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Abstract

The present invention discloses one kind of metal modified HZSM-5 molecular sieve catalyst and its preparation process and application in preparing methyl formate. The metal modified HZSM-5 molecular sieve catalyst is V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Mg, Ba, Ca, Pb, Sn, Mo, W, Sr, Zr, La or Bi modified HZSM-5 molecular sieve catalyst. After the catalyst is set inside a continuously flowing immobilized bed reactor, dimethyl ether, oxygen and inert gas in certain weight proportion are introduced to react at certain temperature to prepare methyl formate. The catalyst results in high dimethyl ether converting rate and high methyl formate yield, and this proves the high reaction activity, high stability and high target product selectivity of the catalyst.

Description

A kind of metal modified HZSM-5-5 molecular sieve catalyst and preparation method thereof and the application in producing methyl formate
Technical field
The present invention relates to a kind of metal modified HZSM-5-5 molecular sieve catalyst, relate to this Preparation of catalysts method, also relate to this catalyst and produce application in the methyl formate in the dimethyl ether catalysis oxidation.
Background technology
Along with the development of World Economics, relative shortage appears in petroleum resources, in this case, is becoming the emphasis that people pay close attention to by the natural gas production chemical product that sets out.Utilize natural gas as raw material at present, obtained substantial breakthrough at next footwork dimethyl ether synthesis of relatively mild condition, thereby realized the process of dimethyl ether, changed dimethyl ether in the past and be the phenomenon that the basis produces, yields poorly, cost is high with methyl alcohol via gas industry production.External dimethyl ether production (is raw material with the oil and natural gas) has at present possessed certain scale, all there is the above dimethyl ether device plan of ten tons of producing per year of establishing in countries such as Japan, Iran and India, and having finished feasibility study, China also is in the starting stage.Along with the various synthetic routes of dimethyl ether be tending towards ripe with and large-scale industrial production day by day realize, the researcher of countries in the world is faced with how to utilize dimethyl ether synthetic be the chemicals problem of raw material traditionally with methyl alcohol always, be studying a question of dimethyl ether reactive chemistry, the Japan and the U.S. have also proposed the notion of " dimethyl ether chemistry " in succession, spare no effort to develop its downstream product.Yet reality is that dimethyl ether is used and is confined to aspects such as aerosol, cold-producing medium, blowing agent and fuel, does not really study on a large scale as industrial chemicals, especially develops research from the catalytic oxidation angle.Therefore, under the current energy situation that the situation is tense, make full use of the resources advantage of dimethyl ether, more useful chemicals or other industrial chemicals are made in the dimethyl ether catalysis oxidation, be of great practical significance undoubtedly.
Methyl formate can participate in the number of chemical synthetic reaction, is a kind of important chemical material.Its industrial process has: direct lipoprotein method, methanol carbonylation and methanol dehydrogenation method.Wherein the direct lipoprotein method is big owing to consumption of raw materials, and the production cost height is superseded substantially; And the formic acid carbonylation method is the industrial process that the present world generally adopts; The methanol dehydrogenation rule is in the middle of the growth, because this method raw material is single, equipment investment is low, and the no three wastes and accessory substance are H 2, industrialized realization will have realistic meaning very.In addition, the method for studying has: synthesis gas one-step synthesis and carbon dioxide and methyl alcohol hydrogenation method etc., and the former is from environmental angle, and the latter will be the synthetic method that has very much DEVELOPMENT PROSPECT from the angle that reduces production costs significantly.
Summary of the invention
The purpose of this invention is to provide a kind of metal modified HZSM-5-5 type molecular sieve catalyst and this Preparation of catalysts method thereof, this catalyst is produced application in the methyl formate reaction in the dimethyl ether catalysis oxidation.
Metal modified HZSM-5 provided by the invention-5 type molecular sieve catalyst is the HZSM-5 type molecular sieve of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Mg, Ba, Ca, Pb, Sn, Mo, W, Sr, Zr, La, Bi modification.
Described catalyst is that metal is supported on the HZSM-5 type molecular sieve, and the loading of metal accounts for 0.1～8% of catalyst gross weight by weight.
Described molecular sieve is a HZSM-5 type molecular sieve, Si/Al=25,38,50.
The preparation method of metal modified HZSM-5 provided by the invention-5 molecular sieve catalyst comprises the steps:
(1) obtain solution: an amount of slaine of weighing is made into the solution of 0.1～1mol/L after with deionized water dissolving respectively;
(2) impregnation process: take by weighing an amount of HZSM-5 molecular sieve, an amount of metal salt solution is taked the method for incipient impregnation, flooded 10～18 hours;
(3) the dry processing: with the molecular sieve of (2) 90～110 ℃ of dryings 3～6 hours in baking oven;
(4) calcination process: (3) are put into Muffle furnace be warming up to 350～650 ℃ and roasting 2～8 hours with the heating rate of 1～3 ℃ of per minute, naturally cool to room temperature then and make modification M/HZSM-5 type molecular sieve catalyst, M represents certain metal.
Molecular sieve catalyst institute carrying metal is the chloride of this metal in the above-mentioned steps (1), earlier chloride is dissolved in excessive ammonia, this metal ion is precipitated fully, isolate precipitation and clean with deionized water, add rare nitric acid and make the precipitation dissolving, carry out above-mentioned steps (2) (3) (4) then.
Molecular sieve catalyst institute carrying metal be the oxide of this metal in the above-mentioned steps (1), adopts polishing, and use ball mill grinding or hand lapping are ground sample after 1 hour and put Muffle furnace into and carry out above-mentioned steps (4).
The application that metal modified HZSM-5 provided by the invention-5 molecular sieve catalyst is produced in the methyl formate reaction in the dimethyl ether catalysis oxidation is that above-mentioned metal modified HZSM-5-5 molecular sieve catalyst is placed in the continuous flow fixed bed reactor, feed a certain proportion of dimethyl ether, oxygen and inert gas, in certain reaction pressure, temperature range, react, produce methyl formate., the mist that described dimethyl ether and oxygen and inert gas are formed feeds in the reaction unit, and dimethyl ether in the mist: oxygen: helium=5: 1: 6, gas space velocity are 3480ml/ (g CataH).
Described oxygen is from air or contain the inert gas of oxygen, and described inert gas is helium or nitrogen.
Described reaction pressure is 0～0.4MP, and described reaction temperature is 150 ℃～500 ℃.
In the reaction of catalytic oxidation dimethyl ether, do not compare with there being catalyst with metal-modified HZSM-5 type molecular sieve catalyst, the conversion ratio of dimethyl ether and the yield of methyl formate all have tangible increase, show that molecular sieve catalyst of the present invention has than high reaction activity and stability and to the high selectivity of target product.
The specific embodiment
Embodiment 1
Take by weighing 2g HZSM-5 molecular sieve (Si/Al=50), with 0.2606g manganese nitrate [Mn (NO 3) 2] solution mixes with it, adopt equi-volume impregnating dipping 12h, put 90 ℃ of oven dry of baking oven 4h again into, put Muffle furnace at last into and be warming up to 500 ℃ of roasting 5h with the heating rate of 3 ℃/min, make the molecular sieve catalyst Mn/HZSM-5 of Mn modification of the present invention, the loading of Mn is 2% (by metal weight).
Activity of such catalysts is estimated in the quartzy fixed-bed reactor of continuous-flow (diameter is 8mm) and is carried out, catalyst screens 40～60 orders behind compressing tablet, and take by weighing 0.2g and put into reactor and react, blank assay adopts blank pipe completely, does not add any catalyst.Catalyst is earlier at 400 ℃ of following O 2The ratio of/He is aging 1h in 1: 5 the gaseous mixture, is cooled to 225 ℃ then and begins reaction, and reaction temperature be that gradient progressively rises to 400 ℃ (blank reactions proceed to 500 ℃) with 25 ℃.Dimethyl ether and oxygen and be 5: 1: 6 as the mol ratio of the helium of carrier gas, reaction velocity is 3480ml/ (g CataH), reaction system pressure is 0.1MPa, reacted product temperature all remains on more than 145 ℃, (the Agilent gas chromatograph GC6820 that U.S. Agilent company produces) adopts the analysis of twin columns method by on-line chromatograph, one is that the Porapak Q packed column of 2m links to each other with the TCD detector, and detect O main the separation 2, CO, CO 2, dimethyl ether (DME), formaldehyde (HCHO), methyl alcohol etc., another root are that the ATSE-30 capillary column of 30m links to each other with fid detector, detect DME, glycol dimethyl ether (DMET), dimethoxym ethane (DMM), dimethyl carbonate (DMC), C main the separation 2H 5OH, methyl formate (MF), methane etc. as bridge, are set up the quantitative relationship of two root chromatogram columns with dimethyl ether.With material carbon number balance is benchmark, calculates conversion ratio, product selectivity and the yield of dimethyl ether.
The distribution situation that mainly contains hydrocarbon product under the differential responses temperature under the table 1 catalyst-free condition
The reflection temperature/℃ DME conversion ratio % Contain C, H selectivity of product % The yield % of MF
C1 C2 C3 MF
250 11.71 34.24 28.29 23.98 17.65 2.07
275 13.69 30.68 21.08 37.42 16.22 2.22
300 12.61 35.73 22.38 29.09 17.62 2.22
325 14.08 36.49 33.81 16.97 15.11 2.12
350 13.37 42.13 31.31 11.45 15.05 2.01
Reaction condition: reaction temperature is from 225 ℃ to 350 ℃, gets a bit every 25 ℃ after 250 ℃.
C1 is mainly methane, methyl alcohol, formaldehyde; C2 is mainly ethanol, MF (methyl formate); C3 is mainly acetone, DMET (glycol dimethyl ether), DMM (dimethoxym ethane)
Table 1 is reflected at the distribution situation that mainly contains hydrocarbon product under the differential responses temperature under the catalyst-free condition, and data show in the table: the conversion ratio of dimethyl ether remains between 11～15%; Product has CO, CO 2, CH 4, CH 3OH, HCHO, MF, C 2H 5OH, acetone and DMET; Conversion ratio is very low before being reflected at 225 ℃, is significantly improved the increase to some extent along with the rising of reaction temperature since 250 ℃; The yield of MF is about 2.2% in product.
Table 2 is for being reflected at the distribution situation that mainly contains hydrocarbon product under the differential responses temperature under the Mn/HZSM-5 catalyst, and data show in the table: under this catalyst, product is based on C1 and C2, low reaction temperatures and higher anti-
The distribution situation that mainly contains hydrocarbon product under the table 2 Mn/H7SM-5 catalyst differential responses temperature
The reflection temperature/℃ DME conversion ratio % Contain C, H selectivity of product % The yield % of MF
C1 C2 C3 MF
250 15.34 34.28 46.47 3.95 28.17 4.32
275 27.81 29.58 16.11 4.39 24.95 6.94
300 22.09 65.81 16.95 2.32 14.57 3.22
325 22.05 61.21 15.08 5.01 6.10 1.34
350 20.27 56.73 9.57 8.46 2.25 0.46
Reaction condition: with table 1
Answer temperature to be unfavorable for the carrying out that reacts, the DME conversion ratio is lower, and along with the rising of reaction temperature, the DME conversion ratio rises, and reaches maximum 27.81% when reaction temperature reaches 275 ℃, and the yield of MF is 6.97%.Reaction temperature continues to raise, and the DME conversion ratio descends thereupon, and the selectivity and the yield of target product also descend.Contrast is investigated this Mn/HZSM-5 catalyst as can be known dimethyl ether catalysis oxidation system methyl formate is had high reaction activity and high and stable and to the high selectivity of target product.
Above data illustrate that all the molecular sieve catalyst of method preparation provided by the invention has the reactivity of dimethyl ether catalysis oxidation system methyl formate preferably.
The distribution situation that mainly contains hydrocarbon product under the table 3 Mg/HZSM-5 catalyst differential responses temperature
The reflection temperature/℃ DME conversion ratio % Contain C, H selectivity of product % The yield % of MF
C1 C2 C3 MF
250 13.75 51.23 23.98 4.58 15.48 2.13
275 20.15 24.56 38.58 15.64 27.79 5.59
300 16.03 33.97 30.32 24.93 17.72 2.84
325 15.24 37.18 32.12 18.52 19.42 2.96
350 15.97 38.03 32.16 16.56 19.58 3.13
Reaction condition: with table 1
Embodiment 2
Take by weighing 2g HZSM-5 molecular sieve (Si/Al=50), with 0.4336g Mg (NO 3) 26H 2O is dissolved in the deionized water, and the preparation method makes the molecular sieve catalyst Mg/HZSM-5 of Mg modification of the present invention with 1, and the loading of Mg is 2% (by metal weight).
Embodiment 3
Take by weighing 2g HZSM-5 molecular sieve (Si/Al=50), with 0.4336g Cu (NO 3) 23H 2O molten with deionized water in be dissolved in the deionized water, the preparation method makes the molecular sieve catalyst Cu/HZSM-5 of Cu modification of the present invention with 1, the loading of Cu is 2% (by metal weight).
The distribution situation that mainly contains hydrocarbon product under the table 4 Cu/HZSM-5 catalyst differential responses temperature
The reflection temperature/℃ DME conversion ratio % Contain C, H selectivity of product % The yield % of MF
C1 C2 C3 MF
250 21.24 44.15 17.64 20.67 17.64 3.75
275 20.25 60.41 17.66 17.66 3.58
300 23.40 68.45 10.76 10.76 2.52
325 26.39 75.14 4.38 4.38 1.16
350 29.01 78.97 1.16 1.16 0.34
Reaction condition: with table 1
Table 3 and table 4 are respectively under Mg/HZSM-5 and the Cu/HZSM-5 catalyst and are reflected at the distribution situation that mainly contains hydrocarbon product under the differential responses temperature, and data show all that catalyst has greater activity to dimethyl ether catalysis oxidation system methyl formate and to the selectivity of target product in the table.
Table 5 different metal modified molecular sieve catalyst mainly contains the distribution situation of hydrocarbon product when reaction temperature is 275 ℃
Catalyst The conversion ratio % of DME Contain C, H selectivity of product % DMET yield %
C1 C2 C3 MF
A 27.81 29.58 16.11 4.39 24.95 6.94
B 20.15 24.56 38.58 15.64 27.79 5.59
C 20.24 60.41 17.66 0 17.66 3.58
A: catalyst A is the catalyst among the embodiment 1; B: catalyst B is the catalyst among the embodiment 2; C: catalyst C is the catalyst among the embodiment 3.
Table 5 item has been listed in the reaction of dimethyl ether catalysis oxidation system methyl formate on the HZSM-5 molecular sieve catalyst of three kinds of different metal Mn, Mg, Cu modification, the reactivity when reaction temperature is 275 ℃.The catalyst that each side's method makes is respectively 27.81%, 20.15%, 20.24% to the conversion ratio of DME, and the yield of target product difference 6.94%, 5.59%, 3.58%.

Claims (10)

1. metal modified HZSM-5-5 molecular sieve catalyst, it is characterized in that: described catalyst is the HZSM-5 type molecular sieve of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Mg, Ba, Ca, Pb, Sn, Mo, W, Sr, Zr, La, Bi modification.
2. metal modified HZSM-5-5 molecular sieve catalyst as claimed in claim 1 is characterized in that: described catalyst is that metal is supported on the HZSM-5 type molecular sieve, and the loading of metal accounts for 0.1～8% of catalyst gross weight by weight.
3. metal modified HZSM-5-5 molecular sieve catalyst as claimed in claim 1 is characterized in that: described HZSM-5 type molecular sieve, Si/Al=25,38,50.
4. the preparation method of metal modified HZSM-5 as claimed in claim 1-5 molecular sieve catalyst is characterized in that comprising the steps: (1) obtain solution: an amount of slaine of weighing is made into the solution of 0.1～1mol/L after with deionized water dissolving respectively;
(2) impregnation process: take by weighing an amount of HZSM-5 molecular sieve, an amount of metal salt solution is taked the method for incipient impregnation, flooded 10～18 hours;
(3) the dry processing: with the molecular sieve of (2) 90～110 ℃ of dryings 3～6 hours in baking oven;
(4) calcination process: (3) are put into Muffle furnace be warming up to 350～650 ℃ and roasting 2～8 hours with the heating rate of 1～3 ℃ of per minute, naturally cool to room temperature then and make modification M/HZSM-5 type molecular sieve catalyst, M represents certain metal.
5. metal modified HZSM-5-5 molecular sieve catalyst preparation method as claimed in claim 4, it is characterized in that: molecular sieve catalyst institute carrying metal is the chloride of this metal in the above-mentioned steps (1), earlier chloride is dissolved in excessive ammonia, this metal ion is precipitated fully, isolate precipitation and clean with deionized water, add rare nitric acid and make the precipitation dissolving, carry out above-mentioned steps (2) (3) (4) then.
6. metal modified HZSM-5-5 molecular sieve catalyst preparation method as claimed in claim 4, it is characterized in that: molecular sieve catalyst institute carrying metal is the oxide of this metal in the above-mentioned steps (1), adopt polishing, use ball mill grinding or hand lapping, grind sample after 1 hour and put Muffle furnace into and carry out above-mentioned steps (4).
7. the application of metal modified HZSM-5 as claimed in claim 1-5 molecular sieve catalyst in producing methyl formate, it is characterized in that: above-mentioned metal modified HZSM-5-5 molecular sieve catalyst is placed in the continuous flow fixed bed reactor, feed a certain proportion of dimethyl ether, oxygen and inert gas, in certain reaction pressure, temperature range, react, produce methyl formate.
8. the application of metal modified HZSM-5-5 molecular sieve catalyst as claimed in claim 7 in producing methyl formate, it is characterized in that, the mist that described dimethyl ether and oxygen and inert gas are formed feeds in the reaction unit, dimethyl ether in the mist: oxygen: helium=5: 1: 6, gas space velocity are 3480ml/g CataH.
9. the application of metal modified HZSM-5-5 molecular sieve catalyst as claimed in claim 7 in producing methyl formate is characterized in that, described oxygen is from air or contain the inert gas of oxygen, and described inert gas is helium or nitrogen.
10. the application of metal modified HZSM-5-5 molecular sieve catalyst as claimed in claim 7 in producing methyl formate is characterized in that described reaction pressure is 0～0.4MP, and described reaction temperature is 150 ℃～500 ℃.
CN 200610035278 2006-04-28 2006-04-28 Metal modified HZSM-5 molecular screen catalyst and its preparation method and uses in preparing methyl formate Pending CN1836778A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101347747B (en) * 2007-07-19 2010-09-15 中国石油化工股份有限公司 Catalyst for producing ethylene by ethanol dehydration and uses thereof
CN102039155A (en) * 2010-11-25 2011-05-04 同济大学 Catalyst for catalytic reforming of waste-plastic pyrolysis oil and preparation method thereof
CN101537369B (en) * 2008-03-21 2012-02-15 上海宝钢化工有限公司 ZSM-5 catalyst and preparation thereof and use thereof
CN102407155A (en) * 2011-11-05 2012-04-11 中国科学院山西煤炭化学研究所 Catalyst for directly preparing ethanol through selective oxidation of dimethyl ether as well as preparation method and application thereof
CN102698792A (en) * 2012-05-31 2012-10-03 潍坊绿霸化工有限公司 Molecular sieve catalyst for producing pyridine base and preparation method thereof
CN102962093A (en) * 2012-11-09 2013-03-13 南京工业大学 Production technique for preparing 2,3-butanedione from 2,3-butanediol by one-step oxidization and heterogeneous catalyst used by same
CN104549443A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Polyformaldehyde dimethyl ether catalyst and application thereof
CN109908948A (en) * 2019-03-25 2019-06-21 北京化工大学 A kind of metal-modified nano-HZSM-5 zeolite catalyst, preparation method and the usage
CN112028949A (en) * 2020-08-31 2020-12-04 安徽师范大学 Method for preparing fructose by glucose catalysis

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101347747B (en) * 2007-07-19 2010-09-15 中国石油化工股份有限公司 Catalyst for producing ethylene by ethanol dehydration and uses thereof
CN101537369B (en) * 2008-03-21 2012-02-15 上海宝钢化工有限公司 ZSM-5 catalyst and preparation thereof and use thereof
CN102039155A (en) * 2010-11-25 2011-05-04 同济大学 Catalyst for catalytic reforming of waste-plastic pyrolysis oil and preparation method thereof
CN102407155A (en) * 2011-11-05 2012-04-11 中国科学院山西煤炭化学研究所 Catalyst for directly preparing ethanol through selective oxidation of dimethyl ether as well as preparation method and application thereof
CN102698792A (en) * 2012-05-31 2012-10-03 潍坊绿霸化工有限公司 Molecular sieve catalyst for producing pyridine base and preparation method thereof
CN102962093A (en) * 2012-11-09 2013-03-13 南京工业大学 Production technique for preparing 2,3-butanedione from 2,3-butanediol by one-step oxidization and heterogeneous catalyst used by same
CN104549443A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Polyformaldehyde dimethyl ether catalyst and application thereof
CN104549443B (en) * 2013-10-28 2017-04-19 中国石油化工股份有限公司 polyformaldehyde dimethyl ether catalyst and application thereof
CN109908948A (en) * 2019-03-25 2019-06-21 北京化工大学 A kind of metal-modified nano-HZSM-5 zeolite catalyst, preparation method and the usage
CN112028949A (en) * 2020-08-31 2020-12-04 安徽师范大学 Method for preparing fructose by glucose catalysis
CN112028949B (en) * 2020-08-31 2021-09-28 安徽师范大学 Method for preparing fructose by glucose catalysis

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