CN1618786A - Method of preparing methylamine by methanol gaseous phase amination - Google Patents
Method of preparing methylamine by methanol gaseous phase amination Download PDFInfo
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- CN1618786A CN1618786A CN 200310108693 CN200310108693A CN1618786A CN 1618786 A CN1618786 A CN 1618786A CN 200310108693 CN200310108693 CN 200310108693 CN 200310108693 A CN200310108693 A CN 200310108693A CN 1618786 A CN1618786 A CN 1618786A
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- vapor phase
- methylamine
- selectivity
- methanol vapor
- described methanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 180
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000005576 amination reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 32
- 239000007792 gaseous phase Substances 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 20
- 239000012808 vapor phase Substances 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229960001866 silicon dioxide Drugs 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052680 mordenite Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 68
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 56
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 238000011835 investigation Methods 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 4
- 229940069446 magnesium acetate Drugs 0.000 description 4
- 235000011285 magnesium acetate Nutrition 0.000 description 4
- 239000011654 magnesium acetate Substances 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000003956 methylamines Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229940001516 sodium nitrate Drugs 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004656 dimethylamines Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
A process for preparing the methylamine from methanol by gas phase amination features the reaction between methanol and ammonia under existance of the catalyst consisting of crystalline silicoaluminate and composition of aluminium oxide and silicon oxide. Its advantages are high catalytic activity and high selectivity.
Description
Technical field
The present invention relates to a kind of methanol vapor phase amination and produce the method for methylamine, more particularly, is the method for using equilibrium catalyst gas phase amination system methylamine with methyl alcohol and ammonia about a kind of.
Background technology
The method of at present domestic and international technical scale synthesis of methylamines generally is at γ-Al
2O
3, Al
2O
3-SiO
2, AlPO, MgO, ThO
2Exist down methyl alcohol and ammonia made by reactor continuously Deng solid acid catalyst, reaction generally be 0.5～4.0Mpa and 350～500 ℃ down reaction make.Reaction product generates three kinds of different methylamines respectively because of the difference of methyl substituted number, i.e. Monomethylamine (MMA), dimethylamine (DMA) and Trimethylamine 99 (TMA).Because the non-crystalline solids acid catalyst does not have the shape of selecting function, reaction product is controlled by thermodynamic(al)equilibrium, and Trimethylamine 99 is the main component of mixture of reaction products stream, growing amount is maximum, as under the typical industry condition (420 ℃, 4.0Mpa, N/C mol ratio=2.5,2.5 hour
-1), the equilibrium composition of this reaction product is: M/D/T=23/27/50 (mole).Though three kinds of methylamines all can be used as the intermediates manufacturing of solvent, medicine, agricultural chemicals, organic synthesis, tensio-active agent etc., but industrial, the product of most worthy is a dimethylamine, and therefore, seeking to improve the dimethylamine overall yield is the target that academia and industry member are seek assiduously for a long time.Before the eighties in 20th century under present industrial route conditions, the main mode of realizing this goal is adjusting process operational condition such as circulation Trimethylamine 99 and Monomethylamine, regulates the feed nitrogen carbon ratio, improves temperature of reaction etc., effect is limited, and makes separating device maximization, energy consumption increase etc.From the nineteen sixty-eight Mobil Hamilton of company patent disclosure crystal aluminosilicate in the dehydration substitution reaction of C1～C5 straight chain alcohol and ammonia, demonstration to one, binary replaces amine has had since the higher selectivity, people have carried out big quantity research to having the zeolite [molecular sieve of selecting the shape effect as methyl alcohol amination system methylamine, and the report of Xiang Guan patent and research document aspect emerges in an endless stream therewith.The disclosed molecular sieve catalyst that is used for this reaction of document has almost covered known all the natural or synthesis of molecular sieve of people.Effect mainly contains preferably: ZSM-5,12,21 (USP4,082,805), ferrierite (USP4,254,061), X, Y, A (USP4,436,938), mordenite (JP416944/1982, JP21005/1984), erionite, chabazite, clinoptilolite (USP253872, JP113747/1981), levyne (EP107457), RHO, ZK-5 (J.Catal.1988,113:367, USP879444, USP4806698, J.Catal.1989,115:79) or the like.The use of these zeolite [molecular sieves is synthetic Monomethylamine of selectivity or dimethylamine to some extent, thereby has reduced the productive rate of Trimethylamine 99.
Though zeolite [molecular sieve can effectively solve most of difficulties that current methylamine industry faces on principle, but (as catalyzer manufacturing cost, use technology, physical strength, life-span) for various reasons, most achievements in research are all also just based on the laboratory scale level in significant period of time, up to nineteen eighty-three, Ri Dong chemical company will spend basic metal that 6 years were developed into and steam and handle combined modified mordenite catalyst and drop into 24000 tons of/year full scale plants in Yokohama and use and drives successfully, indicate the arriving in methylamine shape-selective catalyst epoch.Contemporaneity American Power Convertion Corp., announced that also the methylamine of its exploitation selects shape technology, and had finished the technological transformation (USP4,398,041) of its first cover full scale plant in 1991.All adopting two reactor system is the common feature of this two routine Technology, and reason is that present zeolite shape-selective catalyst does not possess activity of conversion substantially to Trimethylamine 99.Though zeolite catalyst is lower to the Trimethylamine 99 selectivity, long-time running certainly will cause the accumulation of Trimethylamine 99 in system, and influence is to the flexible and the ordinary production of methylamine distribution proportion.In order to address this problem, the conventional catalyst that is subjected to thermodynamic(al)equilibrium control that people's suggestion will be used always is used in combination with a kind of zeolite catalyst, and the two can while or use (JP169445/1982) successively.Day east and APC technology adapt to promptly that this requirement develops.Filling has the zeolite catalyst of selecting the shape function in its first reactor, the conventional silica-alumina catalyst of filling in second reactor, but so both highly selective synthesizing dimethylamines, but flexible methylamine ratio is produced in relative broad range again.
Although selective synthesizing dimethylamine technology has bigger superiority and replaces the inexorable trend of traditional technology, but say as above-mentioned institute, its two reactor system is preferably to newly-built factory, the modernization overlay that old device is then related to production technique, need bigger input, therefore most of methylamine producer is more expected be a kind of can be the raw catalyst that directly uses at existing full scale plant, have higher activity of conversion and suitably improve the dimethylamine selectivity.
Summary of the invention
Technical problem to be solved by this invention is that the equilibrium catalyst in the document existed catalytic activity low in the past, and the problem that the dimethylamine selectivity is low provides a kind of method of new methanol vapor phase amination system methylamine.When this method was used for the methyl alcohol amination, catalyzer had optionally characteristics of advantages of high catalytic activity and dimethylamine.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of methanol vapor phase amination system methylamine, with methyl alcohol and ammonia is reaction raw materials, wherein nitrogen/carbon mol ratio is 0.5～6, in temperature of reaction is 300～450 ℃, reaction pressure is 0.1～6.0MPa, and methyl alcohol air speed GHSV is 500～8000 hours
-1Under the condition, reaction raw materials carries out contact reacts by beds, and wherein used catalyzer contains following component by weight percentage:
A) 5～40% crystal aluminosilicate;
B) 60～95% composite oxides of forming by aluminum oxide and silicon-dioxide, wherein in the composite oxides by weight percentage the amount of silicon-dioxide be 0.5～60%.
In the technique scheme, the consumption preferable range of crystal aluminosilicate is 15～20% by weight percentage, and the crystal aluminosilicate preferred version is selected from least a in mordenite, ZSM-5, β zeolite or the clinoptilolite molecular sieve.The consumption preferable range of the composite oxides of being made up of aluminum oxide and silicon-dioxide is 70～85% by weight percentage, in the composite oxides by weight percentage the amount preferable range of silicon-dioxide be 5～30%, the preferred version pore volume of composite oxides is 0.4～1.3 a milliliter/gram, and preferable range is 0.5～1.0 a milliliter/gram; Specific surface area is 150～500 meters
2/ gram, preferable range is 200～400 meters
2/ gram.The preferred version of catalyzer is also to contain at least a in the compound that is selected from basic metal, alkaline-earth metal, rare earth metal or phosphorus in the catalyzer, and its consumption is 0.001～5% by weight percentage.The temperature of reaction preferable range is 350～420 ℃, and methyl alcohol air speed GHSV preferable range is 1000～5000 hours
-1, nitrogen/carbon mol ratio preferable range is 1.0～3.0.
The Preparation of catalysts method of using in the inventive method adopts common mixing, kneading, extrusion, drying and roasting and gets.
The catalyzer for preparing in the inventive method, available extrusion, compressing tablet or the moulding of spin mode, wherein the crush strength behind the extruded moulding satisfies industrial service requirements fully up to more than 100 newton/0.5 centimetre.
The related main body component of the inventive method is:
Aluminum oxide: silicon content is (with SiO
2Weight % meter, down together) 0.5～60%, preferred 1～40%
Zeolite molecular sieve: mordenite, ZSM-5, β zeolite, clinoptilolite
Alkaline-earth metal, rare earth metal, phosphorus etc. can be SILVER REAGENT or industrial raw material
Used main aluminum oxide of the present invention and the relevant physical parameter of molecular sieve are listed in table 1 and table 2 respectively:
Table 1 aluminum oxide physicals
Aluminum oxide BET, rice
2/ gram pore volume, milliliter/gram aperture, nanometer calcination loss, weight %
Sial＞250 0.7～1.1 4～11 20～30%
Pseudo-boehmite＞200 0.4～0.5 4～5 30%
To ratio aluminum oxide＜100＜0.35＞10 20～30%
Table 2 molecular sieve physicals
| Molecular sieve | Silica alumina ratio | Pore structure | Calcination loss, weight % |
| Mordenite | ??10～25 | 0.65 * 0.70 nanometer (12MR) | ????10 |
| ??ZSM-5 | ????25 | 0.53 * 0.57 nanometer (10MR) | ????10 |
| The β zeolite | ????20 | 0.66 * 0.67 nanometer (12MR) | ????15 |
| Clinoptilolite | ????10 | 0.30 * 0.76 nanometer (12MR) | ????10 |
Catalyzer provided by the invention can carry out methyl alcohol and ammonia amination reaction under 300～450 ℃ (350～420 ℃ of preferable range), N/C in the raw material (mole) is than 0.5～6.0 (preferable range is 1.0～3.0), methyl alcohol air speed GHSV=500～8000 hours
-1, preferred 1000～5000 hours
-1Investigating device is heat-insulating fixed-bed tube reactor (also can be fluidized-bed reactor or shell and tube-type reactor), and stainless steel reactor is of a size of 14 * 2 millimeters of 500 millimeters * φ.During investigation 2 grams are sieved into 12～16 purpose catalyst loadings and go into reactor, be heated to temperature of reaction with tube furnace, react by volume pump charging (compound of methyl alcohol and ammonia), stopping reaction began sampling analysis after 0.5 hour, and exhaust gas component carries out analytical calculation by 102 gas-chromatographies and CDMC-4A totalizing instrument.
According to the total conversion rate (X of methyl alcohol to methylamine
MA) and the selectivity (S of dimethylamine
D), can measure the efficient of catalyzer of the present invention, the methyl alcohol total conversion rate can be by the methyl alcohol that do not transformed in the product amount (mole) and charging in the amount of methyl alcohol compare definitely, selectivity then can be determined the ratio of the carbon mole number of gross product by the mole number of analyzing carbon in the corresponding product.Indication transformation efficiency of the present invention and selectivity are calculated and are undertaken by following A, B two formulas respectively:
X=[1-(in the product in moles of methanol/charging moles of methanol)] * 100% (A)
S
DMA＝{2[DMA]/([MMA]+2[DMA]+3[TMA])}×100％???????????(B)
Above result all calculates based on molal unit.
The present invention is because composite oxides and crystal aluminosilicate that employing is made up of aluminum oxide and silicon-dioxide are catalyzer, and adopt the aluminum oxide of bigger serface, large pore volume to form as catalysis, and adding promotor, make catalyzer can obtain to reach the higher selectivity of equilibrium catalyst of the method acquisition of existing patent disclosure, and have very high transformation efficiency and good operational stability and physical strength than present industrial methylamine catalyst.By evidence, catalyzer of the present invention is at 420 ℃, 2.0Mpa, and under N/C=1.90 (mole) condition, methanol conversion 〉=98.0% (mole, down with), dimethylamine selectivity 〉=30.0% (mole, down with) has been obtained better technical effect.
The present invention is further illustrated with the embodiment of catalyzer provided by the invention below, but these do not provide constraints to the present invention for embodiment." part " all represents parts by weight described in the literary composition unless otherwise noted.
Embodiment
[embodiment 1]
(commercially available, wherein M is a mordenite, SiO to take by weighing 100 gram NaM
2/ Al
2O
3Mol ratio=13) exchange 10 hours through 2～10 times of amount 1N aqueous ammonium nitrate solutions at 95 ℃, suction filtration, washing repeat above process 2～3 times, and molecular sieve is exchanged into ammonium type NH
4M (Na
2O＜0.2 weight %), 130 ℃ of dryings 5 hours, at room temperature exchange 7 hours for 1000 milliliters with the 1N sodium nitrate aqueous solution, the drying calcination process obtains NaHM again.
Take by weighing 13.5 parts of pseudo-boehmites and an amount of diluted nitric acid aqueous solution at whipped state modulated pulp aluminium colloidal sol.Pour above-mentioned aluminium colloidal sol into after getting above-mentioned gained NaHM3.5 part and 27.5 parts of sieve and silica-sesquioxides (siliceous 20 weight %) mixing, evenly mediate, extruded moulding on banded extruder, health is spent the night under the room temperature, 130 ℃ of dryings 6 hours, in 550 ℃ of heat treated 3 hours, pelletizing was shaped to 2 * 1～2 millimeters of φ again, took by weighing 2 these catalyst particles of gram and investigated evaluation, at 420 ℃, N/C mole=1.90,2.0Mpa, methyl alcohol GHSV=4860 hour
-1Under the condition, through reaction in 100 hours, the exhaust sampling analytical results is: methanol conversion was 98.87%, Monomethylamine selectivity 22.14%, dimethylamine selectivity 31.07%, Trimethylamine 99 selectivity 46.79%.
[embodiment 2]
100 gram NaM (commercially available, SiO
2/ Al
2O
3Mol ratio=25) after ammonium friendship, sodium exchange, get 7 parts of these molecular sieves and 27.0 parts of sieve and silica-sesquioxides (siliceous 10 weight %) and 13.5 parts of mixings of pseudo-boehmite with embodiment 1, add rare nitric acid, mediated 15 minutes, drip 2 milliliters of 85% phosphoric acid again, mediated 15 minutes, extruded moulding, health spend the night, 130 ℃ of dryings 6 hours, and 550 ℃ of roastings promptly got modified catalyst in 3 hours.The shaping pelletizing becomes 2 * 1～2 millimeters of φ, gets 2 these catalyzer of gram and investigates with embodiment 1, and the exhaust sampling analytical results is: methanol conversion 99.35%, Monomethylamine selectivity 22.32%, dimethylamine selectivity 31.65%, Trimethylamine 99 selectivity 46.03%.
[embodiment 3]
4.0 part NaM (commercially available, SiO
2/ Al
2O
3Mol ratio=13) through 550 ℃ of roastings 3 hours and 30 parts of sieve and silica-sesquioxides (siliceous 30 weight %) and 0.5 part of magnesium acetate mixing, join in the aluminium colloidal sol of making by 10.5 parts of pseudo-boehmites and an amount of rare nitric acid, fully mediate agglomerating, extrusion, health are dried, make catalyzer and investigation with embodiment 1, the sampling analysis result is: methanol conversion 99.16%, Monomethylamine selectivity 21.37, dimethylamine selectivity 30.81, Trimethylamine 99 selectivity 47.81%.
[embodiment 4]
With 100 the gram NaM (commercially available, SiO
2/ Al
2O
3Mol ratio=20) exchange processing by embodiment 1, get 4 parts of these molecular sieves and 42 parts of sieve and silica-sesquioxides (siliceous 40 weight %), 0.25 part of saltpetre, 15 parts of pseudo-boehmite mixings, add an amount of dilute nitric acid solution, mediate evenly, extrusion, all the other are with embodiment 2, the investigation result is: methanol conversion 98.86%, Monomethylamine selectivity 22.36%, dimethylamine selectivity 31.47%, Trimethylamine 99 selectivity 46.17%.
[embodiment 5]
With 100 the gram NaM (commercially available, SiO
2/ Al
2O
3Mol ratio=10) with getting 5 parts of these molecular sieves and 36 parts of sieve and silica-sesquioxides (siliceous 15 weight %) and 12 parts of pseudo-boehmites, 0.35 part of cerous nitrate mixing after embodiment 1 exchange, add an amount of dilute nitric acid solution, mix and pinch, extrusion, all the other investigate the result: methanol conversion 99.29%, Monomethylamine selectivity 22.35% with embodiment 2, dimethylamine selectivity 30.87%, Trimethylamine 99 selectivity 46.78%.
[embodiment 6]
100 gram NaZSM-5 (commercially available, SiO
2/ Al
2O
3Mol ratio=50) obtain NaHZSM-5 by the exchange of embodiment 1 method, get 8 parts in this molecular sieve and 38 parts of sieve and silica-sesquioxides (siliceous 3 weight %) and make catalyzer with aforementioned method, the investigation result is: methanol conversion 99.36%, Monomethylamine selectivity 21.37%, dimethylamine selectivity 30.56%, Trimethylamine 99 selectivity 48.07%.
[embodiment 7]
(commercially available, wherein β is the β zeolite to 100 gram Na β, SiO
2/ Al
2O
3Mol ratio=30) with getting 4.0 parts of these molecular sieves and 20 parts of sieve and silica-sesquioxides (siliceous 1 weight %) and 12 parts of pseudo-boehmite mixings after the embodiment 1 exchange processing, add an amount of dilute nitric acid solution, mediate extrusion, all the other are with embodiment 2, the investigation result is: methanol conversion 99.16%, Monomethylamine selectivity 22.80%, dimethylamine selectivity 30.72%, Trimethylamine 99 selectivity 46.48%.
[embodiment 8]
100 gram sodium type clinoptilolites (natural, SiO
2/ Al
2O
3Mol ratio=10) make catalyzer by embodiment 6 method stepss, get 2 these catalyzer of gram and investigate 100 hours, the sampling analysis result is: methanol conversion 98.66%, Monomethylamine selectivity 24.11%, dimethylamine selectivity 30.62%, Trimethylamine 99 selectivity 45.27%.
[embodiment 9]
Get 8 parts in embodiment 2 gained NaHM molecular sieves and 40 parts of sieve and silica-sesquioxides (siliceous 5 weight %) and an amount of rare nitric acid, with embodiment 1 preparation catalyzer and investigation, the sampling analysis result is: methanol conversion 99.23%, Monomethylamine selectivity 21.01%, dimethylamine selectivity 30.81%, Trimethylamine 99 selectivity 48.18%.
[embodiment 10]
With 5.0 kilograms of NaHM (by commercially available SiO
2/ Al
2O
3Mol ratio=25NaM obtains by embodiment 1 method exchange) with 26 kilograms of 17.6 kilograms of sieve and silica-sesquioxides (siliceous 35 weight %) and pseudo-boehmites, 150 gram saltpetre, 350 gram magnesium acetate mixings, adding salpeter solution mediated 15 minutes, extrusion, room temperature health are 24 hours on banded extruder, 130 dryings 6 hours, 550 ℃ of roastings got catalyzer in 3 hours.Take a morsel this catalyzer grinds and sieves out 12～16 orders, gets 2 grams and investigates, and the result is: methanol conversion 98.90%, Monomethylamine selectivity 23.03%, dimethylamine selectivity 30.64%, Trimethylamine 99 selectivity 46.33%.
[embodiment 11]
Alumina component is transformed into each 25 kilograms of siliceous 35 weight % sial and pseudo-boehmites among the embodiment 10, all the other are identical, investigate the result to be: methanol conversion 98.81%, Monomethylamine selectivity 25.71%, dimethylamine selectivity 30.82%, Trimethylamine 99 selectivity 43.47%.
[embodiment 12]
Do not add saltpetre among the embodiment 10, all the other together.The investigation result is: methanol conversion 98.87%, Monomethylamine selectivity 24.03%, dimethylamine selectivity 30.57%, Trimethylamine 99 selectivity 45.4%.
[embodiment 13]
Magnesium acetate replaces to cerous nitrate among the embodiment 10, and all the other together.The investigation result is: methanol conversion 98.55%, Monomethylamine selectivity 24.88%, dimethylamine selectivity 30.65%, Trimethylamine 99 selectivity 44.47%.
[embodiment 14]
Remove magnesium acetate among the embodiment 10, all the other together.Investigate the result: methanol conversion 98.63%, Monomethylamine selectivity 25.62%, dimethylamine selectivity 30.78%, Trimethylamine 99 selectivity 43.60%.
[embodiment 15]
Remove saltpetre among the embodiment 10, add 300 gram nitrocalcite, all the other together.Investigate the result: methanol conversion 98.83%, Monomethylamine selectivity 23.0%, dimethylamine selectivity 30.75%, Trimethylamine 99 selectivity 46.25%.
[comparative example 1]
Get 2 certain import equilibrium catalyst of gram and investigate by embodiment 1 condition, the result is as follows: methanol conversion 98.88%, Monomethylamine selectivity 22.81%, dimethylamine selectivity 29.07%, Trimethylamine 99 selectivity 48.12%.
[comparative example 2]
5 parts in embodiment 1 gained molecular sieve with 39 parts to ratio aluminum oxide, 0.35 part of lanthanum nitrate, 0.30 part of SODIUMNITRATE and 0.5 part of lime carbonate mixing, add an amount of rare nitric acid and mediate extrusion, all the other steps are with embodiment 3, the investigation result is: methanol conversion 90.31%, Monomethylamine selectivity 22.13%, dimethylamine selectivity 26.80%, Trimethylamine 99 selectivity 51.07%.
[comparative example 3]
4.5 parts in embodiment 1 gained molecular sieve and 25 parts of pseudo-boehmites and an amount of rare nitric acid are mediated and are made catalyzer, the same investigation, the result is: methanol conversion 98.43%, Monomethylamine selectivity 23.54%, dimethylamine selectivity 27.71%, Trimethylamine 99 selectivity 48.75%.
[embodiment 16]
According to each step and the operational condition of embodiment 1, just changing the N/C mol ratio is 1.0, and reaction pressure is 4.0MPa, and temperature of reaction is 360 ℃, and the methyl alcohol air speed is 1500 hours
-1, its response analysis result is: methanol conversion is 95.2%, and the Monomethylamine selectivity is 23.5%, and the dimethylamine selectivity is 29.1%, and the Trimethylamine 99 selectivity is 47.4%.
[embodiment 17]
According to each step and the operational condition of embodiment 1, just changing the N/C mol ratio is 6.0, and reaction pressure is 1.0MPa, and temperature of reaction is 400 ℃, and the methyl alcohol air speed is 3000 hours
-1, its response analysis result is: methanol conversion is 97.8%, and the Monomethylamine selectivity is 27.2%, and the dimethylamine selectivity is 30.4%, and the Trimethylamine 99 selectivity is 42.4%.
Claims (10)
1, a kind of method of methanol vapor phase amination system methylamine is a reaction raw materials with methyl alcohol and ammonia, and wherein nitrogen/carbon mol ratio is 0.5～6, is 300～450 ℃ in temperature of reaction, and reaction pressure is 0.1～6.0MPa, and methyl alcohol air speed GHSV is 500～8000 hours
-1Under the condition, reaction raw materials carries out contact reacts by beds, it is characterized in that used catalyzer contains following component by weight percentage:
A) 5～40% crystal aluminosilicate;
B) 60～95% composite oxides of forming by aluminum oxide and silicon-dioxide, wherein in the composite oxides by weight percentage the amount of silicon-dioxide be 0.5～60%.
2, according to the method for the described methanol vapor phase of claim 1 amination system methylamine, it is characterized in that the consumption of crystal aluminosilicate is 15～20% by weight percentage, crystal aluminosilicate is selected from least a in mordenite, ZSM-5, β zeolite or the clinoptilolite molecular sieve.
3,, it is characterized in that by weight percentage the consumption of the composite oxides be made up of aluminum oxide and silicon-dioxide is 70～85% according to the method for the described methanol vapor phase of claim 1 amination system methylamine.
4,, it is characterized in that in the composite oxides that the amount of silicon-dioxide is 5～30% by weight percentage according to the method for the described methanol vapor phase of claim 1 amination system methylamine.
5, according to the method for the described methanol vapor phase of claim 1 amination system methylamine, the pore volume that it is characterized in that composite oxides is 0.4～1.3 a milliliter/gram, and specific surface area is 150～500 meters
2/ gram.
6, according to the method for the described methanol vapor phase of claim 5 amination system methylamine, the pore volume that it is characterized in that composite oxides is 0.5～1.0 a milliliter/gram, and specific surface area is 200～400 meters
2/ gram.
7, according to the method for the described methanol vapor phase of claim 1 amination system methylamine, it is characterized in that also containing in the catalyzer at least a in the compound that is selected from basic metal, alkaline-earth metal, rare earth metal and phosphorus, its consumption is 0.001～5% by weight percentage.
8,, it is characterized in that temperature of reaction is 350～420 ℃ according to the method for the described methanol vapor phase of claim 1 amination system methylamine.
9,, it is characterized in that methyl alcohol air speed GHSV is 1000～5000 hours according to the method for the described methanol vapor phase of claim 1 amination system methylamine
-1
10,, it is characterized in that nitrogen/carbon mol ratio is 1.0～3.0 according to the method for the described methanol vapor phase of claim 1 amination system methylamine.
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|---|---|---|---|
| CN 200310108693 CN1252033C (en) | 2003-11-19 | 2003-11-19 | Method of preparing methylamine by methanol gaseous phase amination |
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|---|---|---|---|
| CN 200310108693 CN1252033C (en) | 2003-11-19 | 2003-11-19 | Method of preparing methylamine by methanol gaseous phase amination |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020000165A1 (en) * | 2018-06-26 | 2020-01-02 | Rhodia Operations | Process for the amination of alcohols |
| CN114433086A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and carrier with function of catalyzing alcohol hydroamination to synthesize organic amine, and preparation method and application thereof |
| CN114433113A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and carrier with alcohol catalytic ammoniation function, and preparation method and application thereof |
| WO2023123523A1 (en) * | 2021-12-27 | 2023-07-06 | 山东天成万丰投资有限公司 | Device for producing trimethylamine for synthesizing cation etherifying agent |
-
2003
- 2003-11-19 CN CN 200310108693 patent/CN1252033C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020000165A1 (en) * | 2018-06-26 | 2020-01-02 | Rhodia Operations | Process for the amination of alcohols |
| CN114433086A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and carrier with function of catalyzing alcohol hydroamination to synthesize organic amine, and preparation method and application thereof |
| CN114433113A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and carrier with alcohol catalytic ammoniation function, and preparation method and application thereof |
| CN114433113B (en) * | 2020-10-30 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst and carrier with alcohol ammonification catalysis function, and preparation method and application thereof |
| CN114433086B (en) * | 2020-10-30 | 2024-03-29 | 中国石油化工股份有限公司 | Catalyst and carrier with function of catalyzing hydro-ammonification of alcohol to synthesize organic amine, and preparation method and application thereof |
| WO2023123523A1 (en) * | 2021-12-27 | 2023-07-06 | 山东天成万丰投资有限公司 | Device for producing trimethylamine for synthesizing cation etherifying agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1252033C (en) | 2006-04-19 |
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