CN103028434B - The Catalysts and its preparation method of preparing propylene by methanol transformation - Google Patents

The Catalysts and its preparation method of preparing propylene by methanol transformation Download PDF

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CN103028434B
CN103028434B CN201110293745.8A CN201110293745A CN103028434B CN 103028434 B CN103028434 B CN 103028434B CN 201110293745 A CN201110293745 A CN 201110293745A CN 103028434 B CN103028434 B CN 103028434B
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任丽萍
滕加伟
徐建军
李斌
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a kind of Catalysts and its preparation method of preparing propylene by methanol transformation, mainly solve poor catalyst stability in prior art, problem that Propylene Selectivity is not high.The present invention, by adopting a kind of catalyst of preparing propylene by methanol transformation, in catalyst weight percent, comprises following component: a) SiO of 30 ~ 80% 2/ Al 2o 3the ZSM-5 molecular sieve that silica alumina ratio is 100 ~ 1000, crystallite dimension is 5 ~ 100 nanometers; B) binding agent of 18 ~ 63%; C) 0.05 ~ 5% be selected from least one in Fe, Co, Mo oxide as modifier I; D) 0.01 ~ 2% be selected from the technical scheme of at least one in Ti, V, Cr oxide as modifier II, solve this problem preferably, can be used in the industrial production of preparing propylene from methanol.

Description

The Catalysts and its preparation method of preparing propylene by methanol transformation
Technical field
The present invention relates to a kind of Catalysts and its preparation method for preparing propylene by methanol transformation.
Background technology
Propylene is the important foundation raw material of petro chemical industry, and by the driving that polypropylene and derivative demand thereof increase fast, the demand of a few years from now on propylene will with speed increment faster, and therefore propylene is considered to the product with very big market potentiality.At present, the production method of domestic and international propylene is all raw material with oil, and China's oil resource extremely lacks, and petroleum reserves and output far can not meet the needs of national economy fast development, and imbalance between supply and demand is very severe.By methyl alcohol, to be catalytic material preparing low-carbon olefins (MTO) and methanol conversion preparing propone (MTP) technology be is hopeful the new technology replacing petroleum path most, the key of MTP technology is the development of high performance catalyst, HZSM-5 molecular sieve is because of its suitable aperture and silica alumina ratio adjustable on a large scale, thus become the first-selection of MTP catalyst, under the effect of catalyst, first methyl alcohol dewater generation dimethyl ether, then the equilibrium mixture of methyl alcohol and dimethyl ether continues the low-carbon alkene that is converted into based on ethene and propylene, the low-carbon alkene generated passes through polycondensation, cyclisation, dehydrogenation, the reaction such as alkylation and hydrogen migration generates alkane further, aromatic hydrocarbons and higher olefins.Therefore, improve the diffusion of catalyst, making product rapid diffusion thus reduce side reaction, thus catalyst stability and the selective of product propylene are improved, is the key of MTP catalyst preparation.
Small crystal grain molecular sieve crystal grain is little, duct is short, therefore intracrystalline diffusion resistance is little, be conducive to reactant or product molecule passes in and out molecular sieve pore passage fast, this is highly beneficial to the reaction by diffusion restriction, particularly when reactant and product molecule size and molecular sieve aperture adjoining dimensions, small crystal grain molecular sieve shows larger superiority, the conversion ratio of reaction can be improved on the one hand, on the other hand also because reducing the accumulation of product molecule in duct, and reduce the generation of carbon deposit, the service life of molecular sieve catalyst can be improved, as document (petrochemical industry, 1983, 12 (9): 531) crystallite dimension is found to be the Propylene Selectivity of the ZSM-5 molecular sieve of 0.5 micron higher than crystallite dimension is the ZSM-5 molecular sieve of 3 ~ 5 microns.The molecular sieve that document (catalysis journal, 2004,25 (8): 602) reports little crystal grain has good catalytic stability in the reaction of C 4 olefin cracking propylene.
In addition, the existing a lot of report of modification for ZSM-5 molecular sieve, US Patent No. P3911041, USP4049573, USP4100219 and Japan Patent JP 60-126233, JP 61-97231, JP 62-70324 report respectively and utilize phosphorus, magnesium, silicon and alkali metal to solve the acid control problem of ZSM-5 molecular sieve in preparing propylene from methanol (MTP) reaction, the conversion per pass of methyl alcohol only has 15 ~ 50%, and catalyst stability is bad.LURGI of Germany develops preparing propylene from methanol (MTP) technology (patent WO2004/018089), and its technological principle utilizes modified ZSM-5 catalyst series and fixed bed reactors, and propylene one way is selective is about 35 ~ 40%.CN200810207259.8 reports the reaction of the element modified HZSM-5 molecular sieve catalyst of W for preparing propylene by methanol transformation.
The existing ZSM-5 molecular sieve catalyst for preparing propylene by methanol transformation reaction, exists that propene yield is low, catalyst activity poor stability and the not high shortcoming of Propylene Selectivity.
Summary of the invention
One of technical problem to be solved by this invention is the poor catalyst stability that existing preparing propylene by methanol transformation reacts, the problem that Propylene Selectivity is not high.The invention provides a kind of new preparing propylene by methanol transformation catalysts, when this catalyst is used for preparing propylene by methanol transformation reaction, have that catalyst stability is high, the selective high feature of product propylene.Two of the technical problem that the present invention solves there is provided a kind of preparation method one of solving the problems of the technologies described above propylene catalyst from methanol conversion used.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of preparing propylene by methanol transformation, in catalyst weight percent, comprises following component:
A) SiO of 30 ~ 80% 2/ Al 2o 3silica alumina ratio is 100 ~ 1000 and crystallite dimension is the ZSM-5 molecular sieve of 5 ~ 100 nanometers;
B) binding agent being selected from least one in Ludox, aluminium oxide and aluminum phosphate of 18 ~ 70%;
C) 0.05 ~ 5% be selected from least one in Fe, Co, Mo oxide as modifier I;
D) 0.01 ~ 2% be selected from least one in Ti, V, Cr oxide as modifier II.
In technique scheme, molecular sieve used is silica alumina ratio SiO 2/ Al 2o 3the ZSM-5 molecular sieve that preferable range is 200 ~ 800, crystallite dimension preferable range is 10 ~ 80 nanometers; Modifier I consumption preferable range is 0.05 ~ 2%, and modifier II consumption preferable range is 0.01 ~ 1%.
For solve the problems of the technologies described above two, the preparation method of described propylene catalyst from methanol conversion, comprise following step: (1) is first by nano-ZSM-5 molecular sieve, binding agent and water kneading and compacting, the addition of water so that can kneading be carried out, extrusion is as the criterion, preformed catalyst is the strip of diameter 1.5 ~ 2.0 millimeters, and then drying, 500 ~ 550 DEG C of roastings obtain NaZSM-5 molecular sieve in 4 ~ 8 hours; (2) again NaZSM-5 molecular sieve is exchanged 1 ~ 5 hour in 80 ~ 90 DEG C of ammonium salt aqueous solution, repeat to make ammonium type ZSM-5 molecular sieve 1 ~ 5 time, after 5 hours, obtain HZSM-5 through washing, drying, 550 DEG C of roastings; (3) adopt mass percent concentration be the solubility of 0.05 ~ 2% Fe, Co, Mo salting liquid by HZSM-5 molecular sieve dipping 12 ~ 24 hours, dry 10 ~ 20 hours, 500 ~ 600 DEG C roastings 4 ~ 8 hours in 80 ~ 100 DEG C of baking ovens, obtain the molecular sieve MI-HZSM-5 that modifier I modifies.(4) adopt mass percent concentration be the solubility of 0.01 ~ 1% Ti, V, Cr salting liquid by MI-HZSM-5 molecular sieve dipping 10 ~ 20 hours, dry 5 ~ 10 hours, 500 ~ 600 DEG C roastings 4 ~ 8 hours in 80 ~ 100 DEG C of baking ovens, obtain catalyst for producing propylene with methanol MII MI-HZSM-5.
The using method of above-mentioned catalyst: take methyl alcohol as raw material when using described catalyst preparing propylene, take water as diluent, reacted by the mixture of raw material and diluent with catalyst exposure, obtaining take propylene as the effluent of principal product.When using catalyst water and the mass ratio of methyl alcohol be 0.5 ~ 3: 1, reaction temperature 420 ~ 560 DEG C, methyl alcohol air speed 0.5 ~ 15h -1, reaction pressure 0.01 ~ 1MPa.
At present, there is the problem that catalyst stability is not high, Propylene Selectivity is on the low side in being reacted by preparing propylene by methanol transformation.This is mainly bigger than normal due to ZSM-5 molecular sieve crystallite dimension used, and product diffusion admittance is long, and some large molecular product can not transport out in time from catalyst duct, assemble coking gradually, blocking molecular sieve pore passage, thus catalyst activity is reduced greatly, finally cause catalysqt deactivation.We adopt crystallite dimension to be that the ZSM-5 molecular sieve of 10 ~ 80 nanometers solves this problem, and nano molecular sieve diffusion admittance is short, and product spreads rapidly in molecular sieve pore passage, and large molecular product coking degree obviously reduces, and catalyst stability significantly improves.In addition, adopt the ZSM-5 molecular sieve catalyst of Fe, Co, Mo element and the multiple modification of Ti, V, Cr component, in MTP reaction, there is higher Propylene Selectivity.The catalyst of preparing propylene by methanol transformation of the present invention effectively overcomes the low shortcoming of poor catalyst stability and Propylene Selectivity in prior art, by regulating reaction condition, catalyst stability was more than 1000 hours, and Propylene Selectivity can reach 48%, achieved good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The synthesis of nanometer ZSM molecular sieve adopts conventional hydrothermal synthetic method, with tetrapropyl amine bromide or TPAOH for template, aluminum nitrate or aluminum sulfate are aluminium source, waterglass or ethyl orthosilicate are silicon source, are first fully hydrolyzed by raw material, then transfer in stainless steel autoclave, under suitable salinity and basicity, hydrothermal condition, 80 ~ 150 DEG C of crystallization 30 ~ 100 hours, by different pulp furnish, can obtain silica alumina ratio (SiO 2/ Al 2o 3) be 200 ~ 800, crystallite dimension is the ZSM-5 molecular sieve of l0 ~ 80 nanometer.
[embodiment 2]
Take the NaZSM-5 molecular sieve that 10 grams of silica alumina ratios are 200, crystallite dimension is 80 nanometers, 32 grams of Ludox (SiO 2weight percentage 40%) and 10 grams of aluminum phosphates, add water kneading, with the mould extruded moulding that diameter is 1.5 millimeters, dry, roasting 6 hours in 600 DEG C of air, removes template, exchanges three times in 80 DEG C of ammonium nitrate solutions, in 550 DEG C of roastings 4 hours after oven dry, obtain HZSM-5 molecular sieve catalyst.Be spend the night above-mentioned catalyst 10 grams of incipient impregnations in the ammonium molybdate solution of 0.05% in 30 grams of Mo weight percentages, in 550 DEG C of roastings 4 hours after drying, obtain the nano molecular sieve catalyst Mo-HZSM-5 that 0.15%Mo (weight percentage) modifies.Being impregnated in 10 grams of Ti weight percentages is again in the titanium chloride solution of 0.01% 10 hours, after 100 DEG C of oven dry, in 500 DEG C of Muffle furnace roastings 8 hours, obtain the molecular sieve that 0.01%Ti (weight percentage) modifies, finally obtain the catalyst for producing propylene with methanol consisting of 0.01%Ti0.15%Mo-HZSM-5.
[embodiment 3]
Take the NaZSM-5 molecular sieve that 30 grams of silica alumina ratios are 500, crystallite dimension is 50 nanometers, 38 grams of Ludox (SiO 2weight percentage 40%) and 15 grams of aluminium oxide, add water kneading, with the mould extruded moulding that diameter is 2.0 millimeters, dry, roasting 6 hours in 600 DEG C of air, removes template, exchanges three times in 85 DEG C of ammonium chloride solutions, in 550 DEG C of roastings 4 hours after oven dry, obtain HZSM-5 molecular sieve catalyst.Be spend the night above-mentioned catalyst 10 grams of incipient impregnations in the iron nitrate solution of 1% in 15 grams of Fe weight percentages, in 550 DEG C of roastings 4 hours after drying, obtain the nanometer Fe-HZSM-5 that 1.5%Fe (weight percentage) modifies.Being impregnated in 10 grams of V weight percentages is again in the ammonium metavanadate solution of 0.05% 15 hours, after 80 DEG C of oven dry, in 500 DEG C of Muffle furnace roastings 6 hours, obtain the molecular sieve that 0.05%V (weight percentage) modifies, finally obtain the catalyst for producing propylene with methanol consisting of 0.05V%1.5%Fe-HZSM-5.
[embodiment 4]
Take the NaZSM-5 molecular sieve that 40 grams of silica alumina ratios are 800, crystallite dimension is 10 nanometers, 25 grams of Ludox (SiO 2weight percentage 40%), add water kneading, is the mould extruded moulding of 2.0 millimeters with diameter, dry, roasting 6 hours in 600 DEG C of air, remove template, exchange three times in 90 DEG C of ammonium nitrate solutions, in 550 DEG C of roastings 4 hours after oven dry, obtain HZSM-5 molecular sieve catalyst.Be spend the night above-mentioned catalyst 10 grams of incipient impregnations in the cobalt nitrate solution of 2% in 10 grams of Co weight percentages, in 550 DEG C of roastings 4 hours after drying, obtain the nano Co-HZSM-5 that 2%Co (weight percentage) modifies.Being impregnated in 20 grams of Cr weight percentages is again in the chromium nitrate solution of 0.5% 20 hours, after 80 DEG C of oven dry, in 600 DEG C of Muffle furnace roastings 4 hours, obtain the molecular sieve that 1%Cr (weight percentage) modifies, finally obtain the catalyst for producing propylene with methanol consisting of 1Cr%2%Co-HZSM-5
[embodiment 5]
Take the NaZSM-5 molecular sieve that 10 grams of silica alumina ratios are 800, crystallite dimension is 80 nanometers, 32 grams of Ludox (SiO 2weight percentage 40%) and 10 grams of aluminum phosphates, add water kneading, with the mould extruded moulding that diameter is 1.5 millimeters, dry, roasting 6 hours in 600 DEG C of air, removes template, exchanges three times in 80 DEG C of ammonium nitrate solutions, in 550 DEG C of roastings 4 hours after oven dry, obtain HZSM-5 molecular sieve catalyst.Be spend the night above-mentioned catalyst 10 grams of incipient impregnations in the ammonium molybdate solution of 0.1% in 30 grams of Mo weight percentages, in 550 DEG C of roastings 4 hours after drying, obtain the nanometer Mo-HZSM-5 that 0.3%Mo (weight percentage) modifies.Being impregnated in 10 grams of Cr weight percentages is again in the chromium nitrate solution of 0.5% 20 hours, after 100 DEG C of oven dry, in 600 DEG C of Muffle furnace roastings 4 hours, obtain the molecular sieve that 0.5%Cr (weight percentage) modifies, finally obtain the catalyst for producing propylene with methanol consisting of 0.5Cr%0.3%Mo-HZSM-5.
[embodiment 6]
Take the NaZSM-5 molecular sieve that 30 grams of silica alumina ratios are 500, crystallite dimension is 10 nanometers, 38 grams of Ludox (SiO 2weight percentage 40%) and 15 grams of aluminium oxide, add water kneading, with the mould extruded moulding that diameter is 2.0 millimeters, dry, roasting 6 hours in 600 DEG C of air, removes template, exchanges three times in 85 DEG C of ammonium chloride solutions, in 550 DEG C of roastings 4 hours after oven dry, obtain HZSM-5 molecular sieve catalyst.Be spend the night above-mentioned catalyst 10 grams of incipient impregnations in the cobalt nitrate solution of 1% in 15 grams of Co weight percentages, in 550 DEG C of roastings 4 hours after drying, obtain the nano Co-HZSM-5 that 1.5%Co (weight percentage) modifies.Being impregnated in 20 grams of Ti weight percentages is again in the titanium chloride solution of 0.01% 10 hours, after 80 DEG C of oven dry, in 500 DEG C of Muffle furnace roastings 8 hours, obtain the molecular sieve that 0.02%Ti (weight percentage) modifies, finally obtain the catalyst for producing propylene with methanol consisting of 0.02%Ti1.5%Co-HZSM-5.
[embodiment 7]
Take the NaZSM-5 molecular sieve that 40 grams of silica alumina ratios are 600, crystallite dimension is 80 nanometers, 25 grams of Ludox (SiO 2weight percentage 40%), add water kneading, is the mould extruded moulding of 2.0 millimeters with diameter, dry, roasting 6 hours in 600 DEG C of air, remove template, exchange three times in 90 DEG C of ammonium nitrate solutions, in 550 DEG C of roastings 4 hours after oven dry, obtain HZSM-5 molecular sieve catalyst.Be spend the night above-mentioned catalyst 10 grams of incipient impregnations in the ammonium molybdate solution of 0.2% in 10 grams of Mo weight percentages, in 550 DEG C of roastings 4 hours after drying, obtain the nanometer Mo-HZSM-5 that 0.2%Mo (weight percentage) modifies.Being impregnated in 10 grams of V weight percentages is again in the ammonium metavanadate solution of 0.5% 15 hours, after 100 DEG C of oven dry, in 500 DEG C of Muffle furnace roastings 6 hours, obtain the molecular sieve that 0.5%V (weight percentage) modifies, finally obtain the catalyst for producing propylene with methanol consisting of 0.5V%0.2%Mo-HZSM-5.
[embodiment 8]
Take the NaZSM-5 molecular sieve that 40 grams of silica alumina ratios are 600, crystallite dimension is 80 nanometers, 25 grams of Ludox (SiO 2weight percentage 40%), add water kneading, is the mould extruded moulding of 2.0 millimeters with diameter, dry, roasting 6 hours in 600 DEG C of air, remove template, exchange three times in 90 DEG C of ammonium nitrate solutions, in 550 DEG C of roastings 4 hours after oven dry, obtain HZSM-5 molecular sieve catalyst.Be spend the night above-mentioned catalyst 10 grams of incipient impregnations in the ammonium molybdate solution of 0.2% in 10 grams of Mo weight percentages, in 550 DEG C of roastings 4 hours after drying, obtain the nanometer Mo-HZSM-5 that 0.2%Mo (weight percentage) modifies.Being impregnated in 10 grams of V weight percentages is again in the ammonium metavanadate solution of 0.5% 15 hours, 100 DEG C dry after, in 500 DEG C of Muffle furnace roastings 6 hours, obtain the molecular sieve that 0.5%V (weight percentage) modifies; Being impregnated in 10 grams of zinc weight percentages is again in the ammonium metavanadate solution of 0.2% 10 hours, after 100 DEG C of oven dry, in 500 DEG C of Muffle furnace roastings 3 hours, obtain the molecular sieve that 0.2%Zn (weight percentage) modifies,, finally obtain the catalyst for producing propylene with methanol consisting of 0.2%Zn0.5V%0.2%Mo-HZSM-5.
[embodiment 9]
Adopt fixed-bed catalytic reactor, reactor is stainless steel tube, the evaluation of preparing propylene by methanol transformation reactivity has been carried out to catalyst prepared by [embodiment 2], investigating process conditions used is: catalyst fills 3 grams, operating temperature is 500 DEG C, operating pressure is 0.02MPa, and methanol weight air speed is 1.0h -1, water/methanol weight ratio is 0.5: 1.Appraisal result is as shown in table 1.
Table 1

Claims (5)

1. a catalyst for preparing propylene by methanol transformation, in catalyst weight percent, comprises following component:
A) SiO of 30 ~ 80% 2/ Al 2o 3silica alumina ratio is 100 ~ 1000 and crystallite dimension is the ZSM-5 molecular sieve of 5 ~ 100 nanometers;
B) binding agent being selected from least one in Ludox and aluminium oxide of 18 ~ 70%;
C) the modifier I being selected from least one in Fe, Co oxide of 0.05 ~ 5%;
D) the modifier II being selected from least one in Ti, Cr oxide of 0.01 ~ 2%.
2. the catalyst of preparing propylene by methanol transformation according to claim 1, is characterized in that described ZSM-5 molecular sieve silica alumina ratio SiO 2/ Al 2o 3be 200 ~ 800, crystallite dimension is 10 ~ 80 nanometers; The content of described modifier I is 0.05 ~ 2%, and the content of modifier II is 0.01 ~ 1%.
3. the preparation method of propylene catalyst from methanol conversion described in claim 1, comprises following step:
(1) first by nano-ZSM-5 molecular sieve, binding agent and water kneading and compacting, the addition of water so that can kneading be carried out, extrusion is as the criterion, preformed catalyst is the strip of diameter 1.5 ~ 2.0 millimeters, and then drying, 500 ~ 550 DEG C of roastings obtain NaZSM-5 molecular sieve in 4 ~ 8 hours;
(2) again NaZSM-5 molecular sieve is exchanged 1 ~ 5 hour in 80 ~ 90 DEG C of ammonium salt aqueous solution, repeat to make ammonium type ZSM-5 molecular sieve 1 ~ 5 time, after 5 hours, obtain HZSM-5 through washing, drying, 550 DEG C of roastings;
(3) adopt mass percent concentration be the solubility of 0.05 ~ 2% Fe, Co salting liquid by HZSM-5 molecular sieve dipping 12 ~ 24 hours, dry 10 ~ 20 hours, 500 ~ 600 DEG C roastings 4 ~ 8 hours in 80 ~ 100 DEG C of baking ovens, obtain the molecular sieve MI-HZSM-5 that modifier I modifies;
(4) adopt mass percent concentration be the solubility of 0.01 ~ 1% Ti, Cr salting liquid by MI-HZSM-5 molecular sieve dipping 10 ~ 20 hours, dry 5 ~ 10 hours, 500 ~ 600 DEG C roastings 4 ~ 8 hours in 80 ~ 100 DEG C of baking ovens, obtain catalyst for producing propylene with methanol MII MI-HZSM-5.
4. the preparation method of propylene catalyst from methanol conversion according to claim 3, is characterized in that Fe, Co salting liquid is selected from least one in ferric nitrate or cobalt nitrate.
5. the preparation method of propylene catalyst from methanol conversion according to claim 3, is characterized in that Ti, Cr salting liquid is selected from least one in titanium chloride or chromic nitrate.
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