CN100335458C - Dimethylamine production method - Google Patents
Dimethylamine production method Download PDFInfo
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- CN100335458C CN100335458C CNB2004100460497A CN200410046049A CN100335458C CN 100335458 C CN100335458 C CN 100335458C CN B2004100460497 A CNB2004100460497 A CN B2004100460497A CN 200410046049 A CN200410046049 A CN 200410046049A CN 100335458 C CN100335458 C CN 100335458C
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- dimethylamine
- mordenite
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Abstract
The invention provides a new zeolite catalyst which improves the defect of the conventional zeolite catalyst that the DMA (dimethylamine) selectivity rapidly decreases when the conversion of methanol comes to 95% or more, has a higher methanol consumption reaction activity, and gives a high DMA selectivity and a low TMA (trimethylamine) selectivity.A method for preparing dimethylamine comprises reacting methanol with ammonia, methanol and a methylamine mixture with ammonia or a methylamine mixture with ammonia in the presence of a catalyst in the gas phase, and natural mordenite having a degree of crystallinity of >=40% is used as the catalyst.
Description
Technical field
The invention relates to the use zeolite catalyst,, make the method for dimethylamine by the gas phase contact reacts of methyl alcohol and ammonia.In more detail, be to have the manufacture method of the natural mordenite zeolite of enough degree of crystallinity as the dimethylamine of zeolite catalyst about use.Dimethylamine is important chemical intermediate as the raw material of all kinds of SOLVENTS, pharmaceuticals, rubber chemicals, tensio-active agent etc.
Background technology
General in the presence of the solid acid catalyst of dehydration with aluminum oxide, sial etc. and amination, make methylamine by under gas phase, high temperature (about 400 ℃), methyl alcohol and ammonia being reacted.In this reaction, generate dimethylamine (below, note do DMA), Monomethylamine (below, note is made MMA) and Trimethylamine 99 (below, remember and make TMA).MMA, TMA, it need lack significantly than DMA, after therefore separating from resultant of reaction, is transported in the reaction system and utilizes.
In order from the resultant of reaction of methylamine, to separate dimethylamine, and distill, but TMA and ammonia, MMA, DMA form complicated azeotropic system, and therefore very complicated, large-scale distillation procedure necessitates, and therefore the consumed energy cost of DMA removal process becomes very big.About removal process, for example in " change process drawing complete or collected works " (clear and chemical industrial company of Co., Ltd. distribution on April 25th, 53), detailed description is arranged.
For the reduction that realizes the DMA manufacturing cost and the miniaturization of device, do one's utmost to be suppressed at byproduct methylamine in the reaction, the especially generation of TMA promotes that the generation of DMA is important.But, on common non-crystalline solids an acidic catalyst such as above-mentioned aluminum oxide, sial, the selectivity of 3 kinds of methylamines, by the thermodynamics decision, under common reaction conditions, the production rate of TMA substantially exceeds DMA.
For example, be under the situation of 1: 1 (weight ratio) at the ammonia of 400 ℃ of temperature of reaction, reactor inlet and the ratio of methyl alcohol, generate ratio by the balance of each amine of calculation of thermodynamics, be MMA by the amine carbon ratio: DMA: TMA=0.209: 0.284: 0.507.Therefore, separate a large amount of MMA and TMA usually, carry out to the direction that helps DMA, must in reaction system, carry out recirculation with a large amount of superfluous ammonia that exists in order to make molecular balance ground.
In recent years, be target with the solution of this problem, propose to use various zeolite catalysts.For example, the spy that can enumerate relevant zeolite A open clear 56-69846 number, about the spy of FU-1 open clear 54-148708 number with the special spy who opens clear 58-69846 number, No. the 4082805th, the United States Patent (USP) of relevant ZSM-5, opens clear 56-113747 number, relevant rho, ZK-5 and chabazite about the spy of ferrierite and erionite open clear 61-178951 number with the spy open clear 63-8358 number, the spy of relevant mordenite open clear 56-46846 number, the spy opens clear 59-210050 number and the spy such as opens clear 58-049340 number at various communiques.
Use the method for such zeolite catalyst, though the DMA that exceeds thermodynamic equilibrium value fully is provided selectivity, but the inhibition that DMA selectivity and TMA generate may not be sufficient, and surpass 95～96% as methanol conversion, usually the DMA selectivity just reduces hastily, in order to keep high DMA selectivity, usually there is this problem of the unreacted methanol of the residual a great deal of of having to.For example, open in the clear 59-210050 communique the spy and to disclose, use the Na-mordenite, at methanol conversion is the method that 80～96% scopes selectivity of reacting is made DMA, even this method is in the zeolite catalyst that proposes in the past, also give the good DMA selectivity and the method for methanol consumption reactive behavior.At this, usually N/C is between optimum range 1～2.5, and methanol conversion be more than or equal to 80% condition under, good effect as weight percents, DMA is 53.0%, TMA be 7.7% (methanol conversion: 86.1%, SV:2010) or DMA be 53.9%, TMA be 12.9% (methanol conversion: 94.1%, SV:2020).
In addition, in many cases, active (methanol consumption speed of response) and selectivity can not be existed side by side, and in order to keep highly selective, have to sacrifice activity to a certain degree, perhaps in contrast in order to keep high activity, have to sacrifice selectivity to a certain degree.For example above-mentioned spy opens the embodiment 1 of clear 59-210050 communique, by increasing alkaline kation, makes DMA as weight percents, is increased under 49.3% the situation from 39.5%, and the about 90% o'clock reactive behavior of methanol conversion is reduced to SV1010 from SV2010.Make the method for DMA about the selectivity of using zeolite catalyst, in detailed being described in No. 4,29 volumes " catalyst, 322 pages ".
In methylamine is made, implemented the zeolite catalyst handled by using, as improving optionally method of DMA, be known as following method.Open in the clear 61-254256 communique the spy and to have put down in writing, use the method for the zeolite catalyst of modification, this method is with the compound treatment chabazite, erionite, zeolite rho or the zeolite ZK-5 that contain at least a element that is selected from silicon, aluminium, phosphorus and the boron, on zeolite, precipitate element, but because only use properties-correcting agent, so the properties-correcting agent usage quantity increases, in addition, on the reaction achievement, activity is also little, also low from methyl alcohol to the production rate of methylamine, there are the such problems of by product such as a large amount of generation dme.Open in the flat 11-35527 communique the spy and to have put down in writing, use the method for the catalyzer of in liquid phase, the aluminosilicophosphate silanization being handled.In addition, about mordenite, known have as following method.Open in the clear 59-227841 communique the spy and to have put down in writing, the method of the mordenite catalyst that use is crossed with steam-treated, open in the flat 6-179640 communique the spy and to have put down in writing, the method of the catalyzer that use was handled the mordenite silanization in liquid phase, open in the flat 3-262540 communique the spy and to have put down in writing, use SiCl
4The method of the catalyzer of in gas phase, mordenite being handled, open in flat 8-225498 communique etc. the spy and to have put down in writing, the method of the catalyzer that the solution that use contains sequestrant was handled mordenite, open in the 2000-302735 communique the spy and to have put down in writing, use the method for the mordenite that aluminum ion exchanged etc.
Manufacture method as the DMA that uses the Na-mordenite, open in the clear 56-46846 communique the spy and to have put down in writing, the mordenite that Na amount was regulated in use obtains the method for DMA from the MMA selectivity, open in the clear 59-210050 communique the spy and to have put down in writing, use the mordenite of regulating the Na amount selectively to obtain the method for DMA.In addition,, open in the flat 6-9510 communique the spy and to have put down in writing, use the method for the high mordenite that contains Mg as the manufacture method of the DMA that uses high silicon mordenite.
In addition, open in the flat 8-283207 communique the spy and to have put down in writing, in the crystal habit of mordenite, be conceived to aspect ratio, use this than being methylamine manufacture method more than or equal to 2 bar-shaped mordenite, open in the 2001-38213 communique the spy and to have put down in writing, the mordenite that constitutes smaller or equal to the micropartical of 0.5 μ m with the crystalline particle diameter is made the method for methylamine as the main composition composition.
Summary of the invention
As mentioned above, as the catalyzer that in methylamine is made, uses, though proposed various zeolite catalysts, but the exploitation of zeolite catalyst that can make the DMA of higher output yield while the generation that suppresses TMA in this reaction is main, improves catalytic activity, further improvement, the exploitation of the catalyzer that productive rate rises are expected.
The object of the invention provides, as the catalyzer that in reaction, uses by methyl alcohol or methylamine mixture and ammonia manufacturing dimethylamine, improve as methanol conversion that zeolite catalyst in the past has more than or equal to 95% o'clock, the shortcoming that the DMA selectivity reduces sharp, under higher methanol consumption reactive behavior, give high DMA selectivity and the low optionally novel zeolite catalyst of TMA.
The inventor etc. to achieve the above object, that studies with keen determination found that, during by methyl alcohol or methylamine mixture and ammonia manufacturing dimethylamine, by using the natural mordenite zeolite of degree of crystallinity more than or equal to particular value, and show high methanol consumption reactive behavior, and show high DMA selectivity and low TMA selectivity, thereby finished the present invention.
Promptly, the invention relates to the manufacture method of dimethylamine, it is characterized in that, in the presence of catalyzer, in gas phase, make methyl alcohol and ammonia, methyl alcohol and methylamine mixture and ammonia or methylamine mixture and ammonia react and make the method for dimethylamine, use degree of crystallinity more than or equal to 40% natural mordenite zeolite as catalyzer.
As long as the degree of crystallinity of natural mordenite zeolite is stipulated within the scope of the invention, just can bring into play high reactive behavior, make dimethylamine expeditiously.
Embodiment
Below, explain the present invention.The important point of the present invention is the degree of crystallinity of regulation as the natural mordenite zeolite of catalyzer use.
The so-called natural mordenite zeolite that uses in the present invention is meant that the mordenite of natural product and utilization means chemistry or physics are with the mordenite of the mordenite modified of natural product.In general, contain oblique euthalite (Network リ ノ プ チ Le ラ イ ト), amorphousness, quartz, feldspar, cristobalite, mica etc. as the impurity natural mordenite zeolite.Especially contain a large amount of amorphousness, think that the chemical constitution of its chemical constitution and zeolite is similar.
The degree of crystallinity of so-called natural mordenite zeolite is meant mordenite crystalline and the ratio of removing the mordenite based compound after the crystalline parts such as the quartz that contains impurity in the natural mordenite zeolite, feldspar, can measure with X-ray diffraction, is obtained by following formula 1.
Degree of crystallinity x=(In/Is) * 100
In the formula, In: the scattering strength of natural mordenite zeolite
Is: the scattering strength of synthesizing flokite
In addition, synthesizing flokite uses the Na-MOR-15 of daily output ガ one De ラ corporate system.
The degree of crystallinity of the natural mordenite zeolite of Shi Yonging is more than or equal to 40% in the present invention, is preferably greater than to equal 50%, more preferably greater than equaling 60%.In degree of crystallinity more than or equal to 40% o'clock, can access highly active, even and methanol conversion uprise, do not have DMA optionally sharply to reduce yet, give high DMA selectivity and low TMA optionally catalyzer.Moreover activity of such catalysts can be represented with the represented reaction velocity constant k of formula 2 definition.
Reaction velocity constant K=(FRT/P
oV) * ln{1/ (1-x) }
In the formula, F: methyl alcohol feed speed
R: gas law constant
T: temperature of reaction
P
o: initial stage methyl alcohol dividing potential drop
V: catalyzer capacity
X: methanol conversion
The catalyzer of Shi Yonging in the present invention, the sodium content of preferentially selecting every 100g is the mordenite or the h-mordenite of 0.01g to 2g scope, better sodium content is the scope of 0.1g to 1g.If sodium content too increases, active just reduction, if sodium content too reduces, selectivity just reduces.
The catalyzer of Shi Yonging in the present invention, preferred Si/Al atomic ratio is adjusted to the mordenite of 5 to 9 scopes, the more preferably mordenite of 5.5 to 7 scopes.If the Si/Al atomic ratio is excessive, selectivity just reduces, if too small, the active reduction.In addition, also can be with sequestrant or organo phosphorous compounds mordenite, SiCl with this mordenite modified
4The mordenite handled of CVD.
The catalyzer of Shi Yonging in the present invention, be preferably greater than the particle content that equals the 5mm particle diameter and be 0.1～20 quality %, smaller or equal to the particle content of 2mm particle diameter for smaller or equal to 20 quality %.More than or equal to more preferably 0.2～10 quality % of the ratio of the particle of 5mm, the scope of preferred especially 0.3～5 quality %.In addition, smaller or equal to the ratio of the particle of 2mm preferably smaller or equal to 10 quality %.Though the lower limit smaller or equal to the content of the particle of 2mm can be 0, preferably more than or equal to 0.1 quality %.If the catalyzer more than or equal to the 5mm particle diameter is too much, then active the reduction, if too much smaller or equal to the catalyzer of 2mm particle diameter in addition, it is big and improper that the pressure-losses of reaction tower inner catalyst layer can become.
According to the reaction that the present invention makes dimethylamine, 200～350 ℃ of temperature, preferred 250～330 ℃ scope is carried out.Can be the scope of 0.1～5MPaG, preferred 0.5～3MPaG in reaction pressure, N/C be 1～2.5 scope enforcement than (the nitrogen-atoms number in the reaction system and the mol ratio of carbonatoms).
Below, specifically describe the present invention by embodiment and comparative example, but the present invention is not subjected to any restriction of following examples.
The reaction test method
In the stainless steel reaction pipe of long 800mm, 1/2B, fill the 30ml catalyzer, under 322 ℃ of temperature of reaction, pressure 1.75MPaG, with the speed of per minute 1.05g import ammonia and methyl alcohol etc. the weight mixture, react.
Embodiment 1
In the 2 equivalent hydrochloric acid solns of 1000ml, at 80 ℃ with the natural product mordenite dip treating of degree of crystallinity 64% 8 hours.After the processing, wash,,, obtain H type mordenite thus 570 ℃ of roastings 4 hours 130 ℃ of dryings 4 hours.The Na content of this moment is 0.3 quality %.In addition, as asking size distribution, be 3.8 quality % more than or equal to the catalyzer of 5mm particle diameter from integral distribution curve, be 1.0 quality % smaller or equal to the catalyzer of 2mm particle diameter.Use this mordenite catalyst, carry out the reaction of making dimethylamine by ammonia and methyl alcohol.The 72nd hour the reaction result in reaction beginning back is as follows.
Methanol conversion: 93.1%
Monomethylamine selectivity: 27.3%
Dimethylamine selectivity: 62.9%
Trimethylamine 99 selectivity: 9.9%
Reaction velocity constant k:0.21[1/s]
Embodiment 2
In the 2 equivalent hydrochloric acid solns of 1000ml, the 80 ℃ of natural product mordenite of the 200g with degree of crystallinity 57% dip treating 8 hours.After the processing, wash,,, obtain H type mordenite thus 570 ℃ of roastings 4 hours 130 ℃ of dryings 4 hours.The Na content of this moment is 0.2 quality %.In addition, as asking size distribution, be 4.0 quality % more than or equal to the catalyzer of 5mm particle diameter from integral distribution curve, be 1.3 quality % smaller or equal to the catalyzer of 2mm particle diameter.Use this mordenite catalyst, carry out the reaction of making dimethylamine by ammonia and methyl alcohol.The 72nd hour the reaction result in reaction beginning back is as follows.
Methanol conversion: 92.8%
Monomethylamine selectivity: 28.3%
Dimethylamine selectivity: 60.9%
Trimethylamine 99 selectivity: 10.8%
Reaction velocity constant k:0.20[1/s]
Embodiment 3
In the 2 equivalent hydrochloric acid solns of 1000ml, the 80 ℃ of natural product mordenite of the 200g with degree of crystallinity 46% dip treating 8 hours.After the processing, wash,,, obtain H type mordenite thus 570 ℃ of roastings 4 hours 130 ℃ of dryings 4 hours.The Na content of this moment is 0.2 quality %.In addition, as asking size distribution, be 4.1 quality % more than or equal to the catalyzer of 5mm particle diameter from integral distribution curve, be 1.3 quality % smaller or equal to the catalyzer of 2mm particle diameter.Use this mordenite catalyst, carry out the reaction of making dimethylamine by ammonia and methyl alcohol.The 72nd hour the reaction result in reaction beginning back is as follows.
Methanol conversion: 92.1%
Monomethylamine selectivity: 25.9%
Dimethylamine selectivity: 57.4%
Trimethylamine 99 selectivity: 16.7%
Reaction velocity constant k:0.21[1/s]
Comparative example 1
In the 2 equivalent hydrochloric acid solns of 1000ml, at 80 ℃ with the natural product mordenite 200g dip treating of degree of crystallinity 35% 8 hours.After the processing, wash,,, obtain H type mordenite thus 570 ℃ of roastings 4 hours 130 ℃ of dryings 4 hours.The Na content of this moment is 0.1 quality %.In addition, as asking size distribution, be 4.2 quality % more than or equal to the catalyzer of 5mm particle diameter from integral distribution curve, be 1.5 quality % smaller or equal to the catalyzer of 2mm particle diameter.Use this mordenite catalyst, carry out the reaction of making dimethylamine by ammonia and methyl alcohol.The 72nd hour the reaction result in reaction beginning back is as follows.
Methanol conversion: 86.7%
Monomethylamine selectivity: 25.2%
Dimethylamine selectivity: 45.6%
Trimethylamine 99 selectivity: 29.3%
Reaction velocity constant k:0.17[1/s]
Comparative example 2
Except using amorphous silica-alumina catalyst, temperature of reaction is beyond 380 ℃ and embodiment 1 similarly carries out the reaction of making dimethylamine by ammonia and methyl alcohol.The 3rd hour the reaction result in reaction beginning back is as follows.
Methanol conversion: 98.3%
Monomethylamine selectivity: 20.2%
Dimethylamine selectivity: 24.7%
Trimethylamine 99 selectivity: 54.9%
Reaction velocity constant k:0.32[1/s]
Claims (5)
1. the manufacture method of dimethylamine, it is characterized in that, methyl alcohol and ammonia, methyl alcohol and methylamine mixture and ammonia or methylamine mixture and ammonia react are made in the method for dimethylamine, use degree of crystallinity more than or equal to 40% natural mordenite zeolite as catalyzer.
2. the manufacture method of dimethylamine according to claim 1 is characterized in that, above-mentioned natural mordenite zeolite is that the sodium content of every 100g is the natural mordenite zeolite of 0.01g～2g.
3. the manufacture method of dimethylamine according to claim 1 and 2 is characterized in that, above-mentioned natural mordenite zeolite is that the Si/Al atomic ratio is the natural mordenite zeolite of 5～9 scopes.
4. according to the manufacture method of claim 1,2 or 3 described dimethylamine, it is characterized in that above-mentioned natural mordenite zeolite is that the particle content more than or equal to the 5mm particle diameter is 0.1～20 quality %, is the natural mordenite zeolite smaller or equal to 20 quality % smaller or equal to the particle content of 2mm particle diameter.
5. according to the manufacture method of claim 1,2,3 or 4 described dimethylamine, it is characterized in that, in 200～350 ℃ of temperature, pressure 0.1～5MPaG, N/C than being to carry out gas-phase reaction under the condition of 1～2.5 scope.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003158230 | 2003-06-03 | ||
| JP2003158230A JP2004359581A (en) | 2003-06-03 | 2003-06-03 | Method for preparing dimethylamine |
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| Publication Number | Publication Date |
|---|---|
| CN1572785A CN1572785A (en) | 2005-02-02 |
| CN100335458C true CN100335458C (en) | 2007-09-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004100460497A Expired - Fee Related CN100335458C (en) | 2003-06-03 | 2004-06-01 | Dimethylamine production method |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114308A (en) * | 1994-05-11 | 1996-01-03 | 三井东压化学株式会社 | Process for preparing methylamines |
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2003
- 2003-06-03 JP JP2003158230A patent/JP2004359581A/en active Pending
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- 2004-06-01 CN CNB2004100460497A patent/CN100335458C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114308A (en) * | 1994-05-11 | 1996-01-03 | 三井东压化学株式会社 | Process for preparing methylamines |
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| Publication number | Publication date |
|---|---|
| JP2004359581A (en) | 2004-12-24 |
| CN1572785A (en) | 2005-02-02 |
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Granted publication date: 20070905 Termination date: 20110601 |