CN1285410C - Catalyst for synthesizing dimethylamine from methanol by gas-phase selective amination - Google Patents

Catalyst for synthesizing dimethylamine from methanol by gas-phase selective amination Download PDF

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CN1285410C
CN1285410C CN 200410016380 CN200410016380A CN1285410C CN 1285410 C CN1285410 C CN 1285410C CN 200410016380 CN200410016380 CN 200410016380 CN 200410016380 A CN200410016380 A CN 200410016380A CN 1285410 C CN1285410 C CN 1285410C
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catalyst
hours
silicone oil
dimethylamine
amination
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CN1657167A (en
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姜向东
程文才
杨德琴
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China Petroleum Chemical Co Shanghai Petrochemical
Engineering Research Institute
China Petroleum and Chemical Corp
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China Petroleum Chemical Co Shanghai Petrochemical
Engineering Research Institute
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a catalyst for synthesizing dimethyl amine from methanol by gas-phase selective amination, which mainly solves the problems of low methyl amine and dimethyl amine selectivity and low methanol conversion rate in an equilibrium catalyst in a previous technology. The catalyst of the present invention is composed of crystal silicon aluminate, binding agent aluminum oxide and silicon dioxide dipped and deposed on silicon oil so that the present invention better solves the problems and can be used for the industrial production of methylamine by methanol amination.

Description

The catalyst of methanol vapor phase selectivity amination synthesizing dimethylamine
Technical field
The present invention relates to a kind of catalyst of methanol vapor phase selectivity amination synthesizing dimethylamine.
Background technology
Have several different approach to can be used to improve the selectivity of zeolite catalyst technically, one of them method is carried out " selectionization agent " to zeolite catalyst exactly and is handled modification.
Methylamines and monomethyl amine, dimethylamine and trimethylamine can be used the several different methods manufacturing, but at present industrial widely used be at solid acid catalyst such as Al 2O 3, MgO, SiO 2-Al 2O 3, ThO 2, SAPO etc. exists down, methyl alcohol and ammonia make through the HTHP dehydration, product is subjected to thermodynamics equilibrium limit to be balanced type to distribute, product is based on trimethylamine, and the maximum dimethylamine productive rate of the market demand is very low, causes the contradiction of methylamine production and demand.
Methylamine is important fine chemical material.Difference according to the methyl substituted number of reactant ammonia generates three kinds of methylamines respectively, i.e. monomethyl amine (MMA), dimethylamine (DMA) and trimethylamine (TMA).These methylamines all can be used as the intermediate products of producing multiple solvent, medicine, dyeing assistant, agricultural chemicals and surfactant etc.Even so, the market demand of three kinds of methylamines has very big difference.Under common industrial condition [420 ℃, N/C=2 (mole), 3～5.0MPa] balanced distribution of three kinds of methylamines is: MMA/DMA/TMA=27/23/50 (mole, down together), world market to the demand percentage of three kinds of methylamines is: 21/61/18, the U.S.: 25/57/18, Japan is more up to 10/80/10.
In order to solve the structural inconsistency in the methylamine supply and demand, usually the operation operating mode is optimized in the production, as improving reaction temperature, increase charging ammonia nitrogen ratio, trimethylamine returning charge or the like has improved the yield of dimethylamine to a certain extent, but also brings drawbacks such as the thing energy consumption increases, device maximization.Thereby development of new is efficiently selected the main direction that the shape methylamine catalyst becomes global methylamine subject study.Because this technology is in industrial importance, relevant patent and bibliographical information are too numerous to enumerate, relate to the representational some document patents in field of the present invention and are summarized as follows:
From late 1960s Mobil company deliver introduce the aperture in the patent (US3384667) be the dehydrated aluminosilicate crystal (zeolite) of 5～10 dusts alcohols that is used to have 1～18 carbon with ammonia react can make be major product with monobasic and binary replacement amine since, people recognize that the acidic zeolite with unique regular pore passage structure might solve most of problem of methylamine industry existence.The open report of a large amount of correlative study patents, document has shown the achievement of the synthetic aspect of methylamine shape selective catalysis.The molecular screen material that is used for the methylamine synthetic reaction has almost been included all known natural and synthetic zeolites of people, as natural zeolite faujasite, analcime, clinoptilolite, ferrierite, chabasie, erionite, levyine and modenite etc. are arranged, synthetic zeolite has X, Y, A, modenite, ZSM-5, T zeolite, rho, ZK-5 etc.The use of these zeolite catalysts provides one to improve the selectivity of a dimethylamine, the effective way of minimizing trimethylamine productive rate.But in most cases the direct result of use of zeolite molecular sieve still has suitable distance from expection, judges from industrial point of view, and major defect is that zeolite catalyst selectivity and conversion ratio are economical inadequately, the operational stability deficiency.Therefore people recognize, give full play of the special performance of zeolite molecular sieve, are necessary zeolite molecular sieve is carried out certain modification, to obtain to have the conversion ratio and the selectivity of industrial value, regulate the expection proportion of products as required and distribute.
Because the shape effect of selecting of zeolite mainly has benefited from the sieving actoion of molecular sieve pore passage physical dimension to product molecule, reaction intermediate molecule or reactant molecule, so the effect of pore zeolite such as RHO, ZK-5, chabasie, erionite obviously is better than the molecular sieve of big mesopore such as ZSM-5, modenite, Y, β, clinoptilolite etc.A critical defect of large pore zeolite also is than the easier coking and deactivation of pore zeolite.
Research practice proves that by suitable modification, large pore zeolite such as modenite can obtain good shape selective catalysis effect equally.Disclosed document discloses, and as the technology that a kind of performance that will suppress the trimethylamine generation is effectively given modenite, can use the combination of following one or both or several different methods: 1. suitable cation exchange; 2. outer surface carries out the dealuminzation processing; 3. high-temperature high-pressure steam is handled; 4. the outer surface silylation is handled.
The modification approach of zeolite molecular sieve mainly contains two classes: the one, and molecular sieve surface acidity modulation, promptly change molecular sieve surface acidity intensity, quantity, type and distribution, or cover molecular sieve outer surface highly acid (because of this part activated centre is considered to distribute relevant with the balanced type product usually); Another kind of then is by dwindling the molecular sieve port size, suppressing the macromolecular substances turnover and select the shape effect to reach.Particularly, first kind modification mainly by alkali (soil) metal, rare earth metal [JP49340/1983] as element modified cooperations such as sodium, potassium, calcium, magnesium, lanthanum, ceriums with steam treatment; Second class then mainly can be coated with stain [JP254256/1986] by phosphorus, boron, aluminium, element silicon, and the organic-silicon-modified effect highly significant of especially big molecule can improve the yield of dimethylamine greatly.Aluminium is mended in dealumination complement silicon, desiliconization, steam treatment [JP227841/1984] also is molecular sieve modified effective means, can use separately or be used in combination with other modified method.
EP593086, US5382696 disclose in the presence of the mordenite catalyst of liquid-phase silicone modifying and decorating, with methyl alcohol and ammonia react selective synthesizing dimethylamine, can make trimethylamine reduce to very low-level technology under laboratory scale;
JP262540/1991, US5137854 disclose a kind of method for preparing methylamine catalyst, modenite is earlier through silicon tetrachloride chemical vapor deposition process (CVD), ammonium is handed over into the ammonium type again, the catalyst of Huo Deing has high dimethylamine selectivity and methanol conversion like this, trimethylamine produces hardly, and shortcoming is manufacturing cost height, industrialization difficulty.
JP227841/1984 discloses steam and has handled sieve peg-raking catalyst, has improved monomethyl amine and dimethylamine selectivity, but conversion ratio falls slightly, wherein is better than erionite and clinoptilolite with the modenite effect especially;
The JP179640/1994 of Mitsui, JP59566/1996, JP114725/1998 disclose modenite, the clinoptilolite handled through liquid-phase silicone modification (TEOS, TMOS etc.) and have made catalyst, but high yield dimethylamine, methanol conversion 90% can steady in a long-term be operated.
JP254256/1986 and US4683334 then disclose by silicon, aluminium, phosphorus, boron be deposited on the zeolite and the chabasie of modification, erionite, ZK-5, RHO zeolite as catalyst to reduce the trimethylamine output, shortcoming is to need special synthetic pore zeolite, apart from large-scale industrial production very long process is arranged still.
EP593086 discloses and h-mordenite is carried out the one or many silylanizing has handled the gained catalyst and can make the dimethylamine selectivity reach 64%.But methanol conversion is only about 90%, this means concerning commercial scale, uses this method will need to circulate unconverted methyl alcohol of remarkable quantity.In addition, these results are that cost just obtains by meticulous and complicated technology, as high-temperature calcination for several times in the air, and must careful control modenite water content before the silylanizing.
In sum, though there is the disclosed method of patent that the yield that promotes the expection product is had effect preferably earlier, but belong to laboratory scale pilot study more, most technical matters complexity, manufacturing cost is high, environmental issue is outstanding, repeatedly repeat modification procedure or relate to poisonous harmful reagent as need, it is big etc. that catalyst is unsuitable for large-scale industrial production, low, the easy inactivation of intensity, consumption of raw materials, usually only promoted a dimethylamine selectivity, and on the low side to the activity of conversion of methyl alcohol, industrial uneconomical.Therefore, although be used for having from the catalyst of methyl alcohol or dimethyl ether and ammonia catalysis synthesis of methylamines multiple, but still need to seek a kind of catalyst, it can satisfy simultaneously:
(a) produce high selectivity for the especially desired dimethylamine of a dimethylamine;
(b), preferably approach 100% (mole) and transform needed high activity, thereby avoid recycle methanol with very high methanol conversion;
(c) can carry out large-scale production with simple and economic method.
Summary of the invention
Technical problem to be solved by this invention is that equilibrium catalyst exists one in the conventional art, the dimethylamine selectivity is low, and the problem that methanol conversion is low provides a kind of catalyst of new methanol vapor phase selectivity amination synthesizing dimethylamine.This catalyst is used for methyl alcohol amination system methylamine process and has the methanol conversion height, and one, dimethylamine selectivity height, and the characteristics that can under lower reaction temperature (about 75～100 ℃) condition, operate.
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 methanol vapor phase selectivity amination synthesizing dimethylamine comprises following component in parts by weight:
A) 30～90 parts crystal aluminosilicate, its silica alumina ratio SiO 2/ Al 2O 3Be 5～200;
B) 10～70 parts binding agent aluminium oxide;
C) 0.5～30 part silica;
Wherein silica is by the mode of silicone oil dipping catalyst to be carried out modification, is deposited on the catalyst.
In the technique scheme, in parts by weight, crystal aluminosilicate consumption preferable range is 50～70 parts, and binding agent aluminium oxide consumption preferable range is 30～50 parts, and the silica volume preferable range is 1～15 part.The crystal aluminosilicate preferred version is to be selected from least a in modenite, HZSM-5, β zeolite or the clinoptilolite.The silicone oil preferred version is to be selected from least a in vacuum diffusion pump silicone oil, hydroxy silicon oil, polymethylphenyl siloxane fluid, amido silicon oil, methyl-silicone oil, water-soluble silicon oil, phenyl silicone oil, dimethicone, side chain siloxanes or the octamethylcy-clotetrasiloxane, and the molecular weight preferable range of silicone oil is 500～5000.Silicone oil occupation mode preferred version is to be dissolved in earlier at least a solvent that is selected from water, methyl alcohol, ethanol, isopropyl alcohol, n-hexyl alcohol, n-hexane or the cyclohexane, is deposited on then on the catalyst, and catalyst is carried out modification.
Preparation of catalysts method of the present invention is as follows: at first with crystal aluminosilicate and binding agent aluminium oxide in required ratio mixing, extruded moulding, drying, roasting, flood modification with silicone oil then and form.
The catalyst of the inventive method preparation not only has good catalyst performance, and excellent mechanical intensity is arranged, laboratory small sample (2 * 5 millimeters of φ) crush strength＞90 newton.Having overcome has difficult problems such as inconvenience application that powder-like in the patent or zeolite molecular sieve straight forming cause or mechanical strength deficiency earlier, can satisfy industrial instructions for use.
The method for preparing the methylamine shape-selective catalyst provided by the present invention can be used for the zeolite molecular sieve of silica alumina ratio 5～200 scopes, not only can obtain high dimethylamine selectivity, and very high low-temp methanol conversion ratio is arranged, and significantly reduced catalyst surface coking speed, prolonged catalyst service life.
Method proposed by the invention prepares catalyst, after each dipping silicon compound, with the catalyst roasting, makes organo-silicon compound be decomposed into solid matter (SiO 2) being deposited on catalyst surface, the catalyst roasting can be warming up to more than 250 ℃ by 1 ℃～15 ℃/minute (preferred 2～5 ℃/minute), but must be lower than the temperature that the degree of crystallinity of zeolite is damaged, and generally is lower than 600 ℃, keeps preferred 2～6 hours 1～24 hour.Roasting can directly be carried out in air or oxygen atmosphere.Concrete modification comprises carries out dystopy selectionization processing procedure one time to the molded molecular sieve catalyst carrier, comprises earlier catalyst base being contacted certain hour with a kind of selection agent, carries out this two step of roasting then.
The alleged selection agent of the present invention is multiple commercially available industrial silicone oil, and the listed silicone oil of the present invention does not provide constraints to the present invention.The molecular weight that preferred silicone oil has 500～5000 scopes, viscosity 10～10000mpas.Treat modified molecular sieve catalyst appearance acid sites by chemical means and carry out modification, particularly, be to cover, or the aperture is narrowed down, make macromolecular trimethylamine can't in the hole, form or enter the product main body the inoperative outer surface acidity of expection product center.
The silicon modified catalyst of the present invention's preparation does not generally need to carry out other modification again, but the further modification that the present invention is not limited on this basis is handled.
The modification that the present invention proposes is handled, except can on simple zeolite molecular sieve, carrying out, catalyst with the inventive method modification can also comprise adhesive, and in order to give catalyst satisfied mechanical strength and antiwear property, adhesive can be aluminium type or silicon type or sial type oxide.
According to method provided by the invention, the zeolite molecular sieve that is mixed with adhesive or does not mix adhesive carries out dystopy modification contact (being coated with stain) with a kind of selection agent (preferably organo-silicon compound form), the selectionization agent can directly be used or be scattered in the appropriate solvent, through after the contact of certain hour, with the catalyst roasting to remove the organic principle in carrier and the selectionization agent.
Prepare catalyst according to method proposed by the invention, organo-silicon compound can be before shaping of catalyst, in the moulding or add after the moulding, and the present invention adds after being recommended in moulding.
According to the present invention, selectionization agent consumption is relevant with molecular sieve itself, preferably determines its optimum amount by experiment, and among the present invention, the silicon load capacity is with SiO 2Count 0.5～30 weight %, preferred 1～15 weight %.
Catalyst provided by the invention can be used in the technology of trimethylamine, not returning charge of monomethyl amine, part returning charge or all returning charges.Reactor can be fixed bed adiabatic reactor or fluidized-bed reactor.
Catalyst provided by the present invention, the selectivity of monomethyl amine and dimethylamine can reach more than 75% (mole), wherein dimethylamine＞50% (mole).
It is as follows that the present invention checks and rates the catalyst method:
Get the modified zeolite catalyst particle that 2 grams divide through 12～16 mesh sieves, (bottom is covered with the unidimensional broken magnetic sheet of one deck) 14 * 2 * 500 millimeters stainless steel tubular types of φ reactor reaction section of packing into, 5 * 5 millimeters magnet rings of φ are filled on reactor top, reactor outsourcing heating copper sheathing, place tubular heater, evenly heat temperature raising is to reaction temperature.For guaranteeing that reactant is steam condition when contacting with catalyst, temperature of reactor is reached more than 200 ℃.Except that special mark, the listed test of the present invention is all at 320 ℃, 2.0Mpa, raw material N/C=1.90 (mole), methyl alcohol air speed GHSV=1813 hour -1Under carry out.Reactant feed on demand carbon-nitrogen ratio in advance prepares into liquefied mixture and places high-pressure bottle.
Product is calculated by last minute 102G gas chromatographic analysis after condensation absorbs.
Weigh process efficiency of the present invention, adopting methanol conversion is the total conversion of methylamine and the selectivity that generates each methylamine.As: if only calculate based on the methanol feedstock reactant, total conversion then needs to calculate by following (1) formula by the moles of methanol in unconverted moles of methanol of residue and the charging in the assay products, is shown with percentage table:
Moles of methanol in moles of methanol/charging in the X=[1-product] * 100% (1)
Selectivity to each methylamine is then calculated (molal quantity based on product C calculates) shown in the formula of following (2)～(4) according to the product composition analysis:
S MMA＝{[MMA]/([MMA]+2[DMA]+3[TMA])}×100％ (2)
S DMA＝{2[DMA]/([MMA]+2[DMA]+3[TMA])}×100％ (3)
S TMA＝{3[TMA]/([MMA]+2[DMA]+3[TMA]))×100％ (4)
[MMA], [DMA], [TMA] are respectively the molar content of three kinds of methylamines in the product
The feed molar proportioning is calculated by (5) formula:
N/C=mole NH 3/ mole CH 3OH (5)
The present invention is because with after crystal aluminosilicate and the binding agent mixing extrusion, flooded specific silicone oil again, make it to be deposited on a part that becomes catalyst on the catalyst, confirm through test, the selectivity that catalyst of the present invention is used for its monomethyl amine of methyl alcohol amination system methylamine and dimethylamine can reach more than 75% (mole), wherein dimethylamine selectivity＞50% (mole), and methanol conversion can reach more than 98%, has obtained better technical effect.
The invention will be further elaborated below by embodiment, but be not limited in the restriction of embodiment.
The specific embodiment
[embodiment 1]
Will through pretreated sodium type modenite NaM (commercially available, SiO 2/ Al 2O 3=13) be the NH of 2N, with 2～10 times of amount concentration 4NO 3The aqueous solution exchanges 7～10 hours under 95 ℃ of conditions, the filtration washing filter cake repeats the said process secondary again and gets ammonium type mordenite molecular sieve NH 4M.This molecular sieve 110 ℃ of dryings 6 hours in air, then in muffle furnace 450 ℃ handled 3 hours, promptly obtain acid type modenite HM (Na 2O≤0.1 weight %).
Get above-mentioned gained HM 85 grams, boehmite powder 60 gram and a small amount of mixings of extrusion aid sesbania powder with certain sieve mesh, adding rare nitric acid mixes and to pinch, after the extrusion health at room temperature spend the night, 110 ℃ of dryings 3 hours, 550 ℃ of roastings promptly got catalyst base in 2 hours in muffle furnace then, and pelletizing to be shaped as φ 2 * (1～1.5) mm granules standby.
Get above-mentioned carrier particle 10 grams through 130 ℃ of dryings 6 hours, join 30 milliliters of isopropyl alcohol mixtures that are dissolved with 5 gram vacuum diffusion pump silicone oil, left standstill under the room temperature 24 hours, particle after vacuum filtration diffusion 110 ℃ of dryings 3 hours, be warming up to 450 ℃ with 2 ℃ of/minute clock rate, heat treated promptly got modified catalyst in 3 hours under this temperature.
Get above-mentioned modified catalyst 2 grams and investigate by aforementioned condition, under 320 ℃ through 100 hours reaction backs to reacting the exit gas sample analysis, the result is: methanol conversion X=98.71%, monomethyl amine selectivity S M=27.58%, dimethylamine selectivity S D=56.57%, trimethylamine selectivity S T=15.85%.
[embodiment 2]
Get catalyst base particle 10 grams that embodiment 1 makes, through 130 ℃ of dryings 6 hours, add in 25 milliliters of formed mixed liquors of absolute ethyl alcohol that are dissolved with 3.5 gram hydroxy silicon oils, stir, be coated with stain 24 hours under the room temperature, vacuum filtration diffusion, 130 ℃ of dryings are 3 hours in moving air, are warming up to 500 ℃ of roastings with 3 ℃/minute again and promptly get modified catalyst in 3 hours.
Get above-mentioned modified catalyst 2 grams and investigate with embodiment 1, the reaction beginning is sample analysis reaction exit gas after 100 hours, and the result is: X=98.21%, S M=26.26%, S D=55.15%, S T=18.59%.
[embodiment 3]
100 gram powdery NaM (commercially available, SiO 2/ Al 2O 3=25) carry out ammonium exchange with embodiment 1 and roasting becomes acid type, prepare catalyst base by embodiment 1 method, it is standby that pelletizing is shaped to φ 2 * (1～1.5) millimeter.
Get this carrier particle 10 grams,, join in the 20 ml n-hexane solution that are dissolved with 2.5 gram polymethylphenyl siloxane fluids, stir this suspension, left standstill 24 hours, make modified catalyst by embodiment 2 through 130 ℃ of dryings 6 hours.Investigated analysis through 100 hours, the result is: X=98.61%, S M=25.92%, S D=53.45%, S T=20.63%.
[embodiment 4]
Get 10 gram embodiment, 1 prepared catalyst base particle, through 130 ℃ of dryings 6 hours, add in the 20 ml n-hexane solution that are dissolved with 2.5 gram amido silicon oils 8460, stir, left standstill under the room temperature 24 hours, vacuum filtration diffusion, particle is warming up to 500 ℃ of roastings with 3 ℃/minute again and promptly got modified catalyst in 3 hours 110 ℃ of dryings 3 hours.
Investigate with embodiment 1, react sample analysis after 100 hours, the result is: X=98.23%, S M=27.75%, S D=52.69%, S T=19.56%.
[embodiment 5]
Carry out modification with embodiment 3 gained catalyst base particles 10 grams, the agent of modification selectionization is 20 milliliters of absolute methanol solutions that are dissolved with methyl-silicone oil 1.5 grams, and the modification procedure method is with embodiment 3.
Investigate 100 hours with embodiment 1, the result is: X=98.05%, S M=29.14%, S D=50.63%, S T=20.23%.
[embodiment 6]
Preparation process is with embodiment 4, and difference is that the agent of modification selectionization is the 30 ml deionized water solution that are dissolved with 5 gram water-soluble silicon oils.
80 hours results of the same investigation are: X=99.30%, S M=28.54%, S D=50.07%, S T=21.39%.
[embodiment 7]
Carry out modification with 10 gram embodiment, 1 gained carrier particle by embodiment 2 method steps, difference is that the agent of modification selectionization is 15 milliliters of toluene solutions that are dissolved with 2.0 gram phenyl silicone oil.
The same investigation 100 hours, the result is: X=96.63%, S M=28.37%, S D=51.87%, S T=19.76%.
[embodiment 8]
Carrier preparation and modification procedure are with embodiment 3, and difference is that the agent of modification selectionization is to be dissolved with 20 milliliters of the absolute methanol solutions of 1.0 gram phenyl methyl silicone oils.
Investigated through 100 hours, analysis result is: X=96.25%, S M=29.38%, S D=50.22%, S T=20.40%.
[embodiment 9]
Catalyst base preparation and modification procedure are with embodiment 3, and difference is that the agent of modification selectionization is 20 milliliters of absolute methanol solutions that are dissolved with 1.5 gram dimethicones.
Investigated through 100 hours, analysis result is: X=97.92%, S M=27.63%, S D=50.97%, S T=21.40%.
[embodiment 10]
Catalyst base preparation and modification procedure are with embodiment 3, and difference is that the agent of modification selectionization is 30 milliliters of absolute methanol solutions that are dissolved with 5.0 gram octamethylcy-clotetrasiloxanes.
Investigated through 100 hours, analysis result is: X=98.19%, S M=30.63%, S D=50.88%, S T=18.49%.
[embodiment 11]
Catalyst base preparation and modification procedure are with embodiment 3, and difference is that the agent of modification selectionization is 20 milliliters of ethanol solutions that are dissolved with 2.0 gram side chain siloxanes.
Investigated through 100 hours, analysis result is: X=97.22%, S M=26.49%, S D=51.66%, S T=22.91%.
[embodiment 12]
100 gram sodium type ZSM-5 molecular sieves (commercially available, SiO 2/ Al 2O 3Mol ratio=60) powder suspension is in the aqueous ammonium nitrate solution of 3N in 1000 ml concns, stir exchange 7 hours down at 95 ℃, with 10 times of water yield washing leaching cakes and suction filtration drying, repeat this process and obtain ammonium type ZSM-5 for 2 times, through 130 ℃ of dryings 3 hours, 550 ℃ of roastings obtained acid type ZSM-5 molecular sieve in 2 hours again.
Take by weighing 22 gram boehmites and add the powerful stirring of rare nitric acid 30 minutes, be modulated into aluminium colloidal sol, the above-mentioned gained acid type ZSM-5 molecular sieve of 35 grams is added, and pelletizing is shaped to φ 2 * (1～1.5) millimeter after kneading, extrusion, health, drying, roasting, obtains catalyst base.
Get above-mentioned carrier particle 10 grams and after 6 hours, drip 6.0 gram vacuum diffusion pump silicone oil while stirring, dropwise and continue to stir 15 minutes through 130 ℃ of dryings, standing over night under the room temperature, the vacuum filtration diffusion places muffle furnace to be warming up to 450 ℃ of heating 3 hours with 2 ℃/minute, promptly gets modified catalyst.Investigate with embodiment 1, the post analysis result was in 100 hours: X=97.88%, S M=25.40%, S D=53.12%, S T=21.48%.
[embodiment 13]
100 gram sodium type β zeolites (commercially available, SiO 2/ Al 2O 3Mol ratio=30), make catalyst base and carry out modification by embodiment 12 modes, modification procedure is with embodiment 12, and difference is that the agent of modification selectionization is 5 gram hydroxy silicon oils.
The analysis result of investigating after 100 hours with embodiment 1 is: X=96.83%, S M=26.50%, S D=50.39%, S T=23.11%.
[embodiment 14]
50 grams, 12～16 order sodium type using natural clinoptilolite particles that sieve out (commercially available, SiO 2/ Al 2O 3Mol ratio=10) make acid type clinoptilolite molecular sieve carrier by embodiment 12 methods.Get this carrier particle 10 grams, join in 30 milliliters of cyclohexane solutions that are dissolved with 9 gram methyl-silicone oils, form suspension, fully stir, at room temperature standing over night is carried out vacuum filtration diffusion, drying to suspension, promptly obtained modified catalyst in 3 hours 500 ℃ of roastings again, investigate with embodiment 1, reaction post analysis result was in 80 hours: X=96.20%, S M=28.14%, S D=50.78%, S T=21.08%.
[embodiment 15]
100 gram NaM (commercially available, SiO 2/ Al 2O 3Mol ratio=25) hand over into ammonium type molecular sieve NH by embodiment 3 method ammoniums 4M (Na 2O≤0.1 weight %).Get 70 these ammonium type molecular sieves of gram,, add a certain amount of rare nitric acid and mediated 15 minutes with 35 gram boehmite mixings, drip 6 gram vacuum diffusion pump silicone oil again, continue to mediate 15 minutes, extrusion, health are spent the night, 110 ℃ of dryings 6 hours promptly got modified catalyst in 3 hours through 550 ℃ of roastings again.Pelletizing is shaped as φ 2 * (1～1.5) millimeter, gets 2 these catalyst of gram and investigates with embodiment 1 condition, reacts 100 hours results and is: X=98.30%, S M=28.14%, S D=54.11%, S T=17.75%.
[embodiment 16]
With embodiment 1 gained HM catalyst base particle 10 grams, drip 2.5 gram polymethylphenyl siloxane fluids, stirring is coated with stain, left standstill under the room temperature 24 hours, suction filtration diffusion, drying are rapidly heated to 500 ℃ with 15 ℃/minute, and promptly got modified catalyst in 3 hours at this roasting temperature.Get 2 these catalyst of gram and ditto investigate, react 100 hours results and be: X=98.70%, S M=25.34%, S D=50.40%, S T=24.26%.
[comparative example 1]
100 gram NaM (commercially available, SiO 2/ Al 2O 3Mol ratio=25) be exchanged into ammonium type NH by embodiment 3 ammonium friendship conditions 4M, 110 ℃ of dryings became acid type HM in 2 hours in 550 ℃ of roastings after 3 hours again.Getting these HM 33 grams joins in 750 milliliters of ethanol solutions that are dissolved with 5 gram TEOS, vibration was stirred this suspension 24 hours under 50 ℃ of constant temperatures of oil bath, filter the HM that collects wherein, and with 500 milliliters of washings of absolute ethyl alcohol, 110 ℃ of dryings are after 3 hours, 300 ℃ were heated 3 hours under flowing nitrogen atmosphere, 500 ℃ of roastings 2 hours in air then, with gained modified molecular screen like this and 15 gram boehmites and rare nitric acid kneading extrusion, dry, roasting obtains modified catalyst, pelletizing is shaped as φ 2 * (1～1.5) millimeter, get 2 these catalyst of gram and ditto investigate, react 100 hours results and be: X=95.66%, S M=24.59%, S D=41.20%, S T=34.21%.
[comparative example 2]
Get 10 gram embodiment, 1 gained HM carrier particle, dropwise add 5 gram amido silicon oils, be coated with stain evenly, placed 24 hours under the room temperature, the vacuum filtration diffusion obtained final catalyst in 3 hours with 5 ℃ of/minute temperature to 550 ℃ of roastings.Investigate with embodiment 1 with these catalyst 2 grams, react sample analysis after 100 hours, the result is: X=97.72%, S M=27.12%, S D=50.47%, S T=22.41%.
Get 10 gram embodiment, 1 gained HM carrier particle, dropwise add 3 gram amido silicon oils, stirring is coated with stain evenly, at room temperature left standstill 24 hours, suction filtration diffusion, drying are warming up to 550 ℃ of roastings 2 hours with 5 ℃/minute, the gained particle repeat again above be coated with the stain and heat treatment process once promptly get final modified catalyst, the same contrast is investigated, and reacts 60 hours results and is: X=92.83%, S M=30.74%, S D=40.31%, S T=28.95%.
[comparative example 3]
100 gram NaM (commercially available, SiO 2/ Al 2O 3Mol ratio=10) hand over into ammonium type molecular sieve NH with embodiment 1 condition ammonium 4M and 130 ℃ of dryings 6 hours.Take by weighing these ammonium type molecular sieve 47 grams and 26 gram boehmite mixings, add rare nitric acid, kneading, extrusion, health, drying obtained catalyst A in 3 hours through 550 ℃ of roastings again, and pelletizing is shaped as φ 2 * (1～1.5) millimeter.Get these catalyst particle 2 grams and investigate by aforementioned condition (350 ℃), react sample analysis exit gas composition after 60 hours, the result is: X=98.56%, S M=21.09%, S D=33.18%, S T=45.73%
Get above-mentioned gained catalyst particle 10 grams, through 130 ℃ of dryings 6 hours, added 20 milliliters of dippings of 10 weight % lanthanum nitrate hexahydrates 24 hours, suction filtration, washing, drying, 550 ℃ of roastings made modified catalyst B in 2 hours.50 hours results of the same investigation are: X=97.98%, S M=23.48%, S D=40.77%, S T=35.75%
[comparative example 4]
With embodiment 3 gained acid type molecular sieve HM 28.5 grams and 15 gram boehmite mixings, add rare nitric acid, kneading extrusion, health are spent the night, 3 hours, 550 ℃ roastings of 110 ℃ of dryings got catalyst C in 3 hours, and pelletizing is shaped to φ 2 * (1～1.5) millimeter.Get these particle 2 grams and investigate (330 ℃) 50 hours, analysis result is: X=97.75%, S M=23.65%, S D=29.48%, S T=48.87%
Get above-mentioned acid type HM 25 grams, mix with 13 milliliter of 40% Ludox pinch, extrusion, drying, roasting, pelletizing shaping (the same) catalyst D.50 hours analysis result: X=96.49% of the same investigation, SM=22.04%, SD=41.35%, ST=37.11%

Claims (6)

1, a kind of catalyst of methanol vapor phase selectivity amination synthesizing dimethylamine comprises following component in parts by weight:
A) 30～90 parts crystal aluminosilicate, its silica alumina ratio SiO 2/ Al 2O 3Be 5～200;
B) 10～70 parts binding agent aluminium oxide;
C) 0.5～30 part silica;
Wherein silica is by the mode of silicone oil dipping catalyst to be carried out modification, is deposited on the catalyst.
2, according to the catalyst of the described methanol vapor phase selectivity of claim 1 amination synthesizing dimethylamine, it is characterized in that in parts by weight the crystal aluminosilicate consumption is 50～70 parts, binding agent aluminium oxide consumption is 30～50 parts, and silica volume is 1～15 part.
3,, it is characterized in that crystal aluminosilicate is to be selected from least a in modenite, HZSM-5, β zeolite or the clinoptilolite according to the catalyst of the described methanol vapor phase selectivity of claim 1 amination synthesizing dimethylamine.
4,, it is characterized in that silicone oil is selected from least a in vacuum diffusion pump silicone oil, hydroxy silicon oil, polymethylphenyl siloxane fluid, amido silicon oil, methyl-silicone oil, water-soluble silicon oil, phenyl silicone oil, dimethicone, side chain siloxanes or the octamethylcy-clotetrasiloxane according to the catalyst of the described methanol vapor phase selectivity of claim 1 amination synthesizing dimethylamine.
5, according to the catalyst of the described methanol vapor phase selectivity of claim 1 amination synthesizing dimethylamine, the molecular weight that it is characterized in that silicone oil is 500～5000.
6, according to the catalyst of the described methanol vapor phase selectivity of claim 1 amination synthesizing dimethylamine, it is characterized in that silicone oil is to be dissolved in earlier at least a solvent that is selected from water, methyl alcohol, ethanol, isopropyl alcohol, n-hexyl alcohol, n-hexane or the cyclohexane, be deposited on then on the catalyst, catalyst is carried out modification.
CN 200410016380 2004-02-18 2004-02-18 Catalyst for synthesizing dimethylamine from methanol by gas-phase selective amination Expired - Lifetime CN1285410C (en)

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