CN1618517A - Catalyst used for gas-phase amination of methanol and ammonium to produce methylamine - Google Patents
Catalyst used for gas-phase amination of methanol and ammonium to produce methylamine Download PDFInfo
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- CN1618517A CN1618517A CN 200310108694 CN200310108694A CN1618517A CN 1618517 A CN1618517 A CN 1618517A CN 200310108694 CN200310108694 CN 200310108694 CN 200310108694 A CN200310108694 A CN 200310108694A CN 1618517 A CN1618517 A CN 1618517A
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- Prior art keywords
- catalyst
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- methylamine
- methyl alcohol
- amination
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 135
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims description 56
- 238000005576 amination reaction Methods 0.000 title claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 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
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 6
- 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
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 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
- 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
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 64
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 54
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000000034 method Methods 0.000 description 11
- 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
- 239000000047 product Substances 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
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- 239000011654 magnesium acetate Substances 0.000 description 4
- 229940069446 magnesium acetate Drugs 0.000 description 4
- 235000011285 magnesium acetate Nutrition 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- 239000000203 mixture Substances 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
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000003956 methylamines Chemical class 0.000 description 3
- 238000002360 preparation method Methods 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
- 238000005303 weighing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- -1 organic synthesis Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 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
- 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
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst 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
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000013067 intermediate product 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
- 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
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 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
- 238000003756 stirring Methods 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
A catayst for preparing methylamine from methanol and ammonia by gas-phase ammoniation is composed of crystalline silicoaluminate and the composite oxide prepared from alumina and SiO2. Its advantage is high catalytic activity and selectivity.
Description
Technical field
The present invention relates to a kind of be used for methyl alcohol and ammonia mutually amination produce the catalyst of methylamine, more particularly, be about a kind of with methyl alcohol and ammonia mutually amination produce the equilibrium catalyst of methylamine.
Background technology
The method of at present domestic and international commercial 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.Product generates three kinds of different methylamines respectively because of the difference of methyl substituted number, i.e. monomethyl amine (MMA), dimethylamine (DMA) and trimethylamine (TMA).Because the non-crystalline solids acid catalyst does not have the shape of selecting function, product is controlled by thermodynamical equilibrium, and trimethylamine 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 product is: M/D/T=23/27/50 (mole).Though three kinds of methylamines all can be used as the intermediate products manufacturing of solvent, medicine, agricultural chemicals, organic synthesis, surfactant etc., but industrial, the product of most worthy is a dimethylamine, and therefore, seeking to improve the dimethylamine gross production rate is the target that academia and industrial quarters 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 operating condition such as circulation trimethylamine and monomethyl amine, regulates the feed nitrogen carbon ratio, improves reaction temperature etc., effect is limited, and makes separation equipment 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 catalyst 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 all known 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), modenite (JP416944/1982, JP21005/1984), erionite, chabasie, clinoptilolite (USP253872, JP113747/1981), levyine (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 sieve catalysts is synthetic monomethyl amine of selectivity or dimethylamine to some extent, thereby has reduced the productive rate of trimethylamine.
Though zeolite molecular sieve catalyst can effectively solve most of difficulties that current methylamine industry faces on principle, but (as catalyst manufacturing cost, use technology, mechanical 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 alkali metal that 6 years were developed into and steam and handle combined modified mordenite catalyst and drop into 24000 tons of/year commercial 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 commercial 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.Though zeolite catalyst is lower to the trimethylamine selectivity, long-time running certainly will cause the accumulation of trimethylamine in system, and influence is to the flexible modulation and the ordinary production of methylamine distribution proportion.In order to address this problem, the conventional catalyst that is subjected to thermodynamical 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 high selectivity synthesizing dimethylamines, but flexible modulation methylamine ratio is produced in relative broad range again.
Although selective synthesizing dimethylamine technology has bigger superiority and replaces the inexorable trend of traditional handicraft, 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 technology, need bigger input, what therefore most of methylamine producer was more expected is a kind of raw catelyst that can directly use on existing commercial 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 new methyl alcohol and ammonia catalyst of amination production methylamine mutually that is used for.This catalyst has optionally characteristics of advantages of high catalytic activity and dimethylamine when being used for the methyl alcohol amination.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of be used for methyl alcohol and ammonia mutually amination produce the catalyst of methylamine, contain following component by weight percentage:
A) 5～40% crystal aluminosilicate;
B) 60～95% composite oxides of forming by aluminium oxide and silica, wherein in the composite oxides by weight percentage the amount of silica 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 modenite, ZSM-5, β zeolite or the clinoptilolite molecular sieve.The consumption preferable range of the composite oxides of being made up of aluminium oxide and silica is 70～85% by weight percentage, in the composite oxides by weight percentage the amount preferable range of silica be 5～30%, the preferred version pore volume of composite oxides is 0.4～1-3 milliliter/gram, and preferable range is 0.5～1.0 a milliliter/gram; Specific area is 150～500 meters
2/ gram, preferable range is 200～400 meters
2/ gram.The preferred version of catalyst is also to contain at least a in the compound that is selected from alkali metal, alkaline-earth metal, rare earth metal or phosphorus in the catalyst, and its consumption is 0.001～5% by weight percentage.
Preparation of catalysts method of the present invention adopts common mixing, kneading, extrusion, drying and roasting and gets.
The catalyst of the present invention preparation, available extrusion, compressing tablet or the moulding of spin mode, wherein the crush strength behind the extruded moulding satisfies industrial instructions for use fully up to more than 100 newton/0.5 centimetre.
The related main body component of catalyst of the present invention is:
Aluminium oxide: silicon content is (with SiO
2Weight % meter, down together) 0.5～60%, preferred 1～40%
Zeolite molecular sieve: modenite, ZSM-5, β zeolite, clinoptilolite
Alkaline-earth metal, rare earth metal, phosphorus etc. can be SILVER REAGENT or industrial raw material
Used main aluminium oxide of the present invention and the relevant physical parameter of molecular sieve are listed in table 1 and table 2 respectively:
Table 1 aluminium oxide physical property
Aluminium oxide BET, rice
2/ gram pore volume, milliliter/gram aperture, nanometer calcination loss, weight %
Sial＞250 0.7～1.1 4～11 20～30%
Boehmite＞200 0.4～0.5 4～5 30%
To ratio aluminum oxide＜100＜0.35＞10 20～30%
Table 2 molecular sieve physical property
| Molecular sieve | Silica alumina ratio | Pore structure | Calcination loss, weight % |
| Modenite | ??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 |
Catalyst provided by the invention can carry out methyl alcohol and ammonia aminating 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 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 and be packed into reactor, be heated to reaction temperature with tube furnace, react by measuring pump charging (compound of methyl alcohol and ammonia), stopping reaction began sample analysis after 0.5 hour, and exhaust gas component carries out analytical calculation by 102 gas-chromatographies and CDMC-4A integrator.
According to the total conversion (X of methyl alcohol to methylamine
MA) and the selectivity (S of dimethylamine
D), can measure the efficient of catalyst of the present invention, the methyl alcohol total conversion 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 conversion ratio 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 aluminium oxide and silica are catalyst, and adopt the aluminium oxide of bigger serface, large pore volume to form as catalysis, and adding co-catalyst, make catalyst can obtain to reach the higher selectivity of equilibrium catalyst of the method acquisition of existing patent disclosure, and have very high conversion ratio and good operational stability and mechanical strength than present industrial methylamine catalyst.By evidence, catalyst 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 catalyst 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.
The specific embodiment
[embodiment 1]
(commercially available, wherein M is a modenite, 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 boehmites and an amount of diluted nitric acid aqueous solution at stirring 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, GHSV=4860 hour
-1Under the condition, through reaction in 100 hours, the exhaust sampling analysis result is: methanol conversion was 98.87%, monomethyl amine selectivity 22.14%, dimethylamine selectivity 31.07%, trimethylamine 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 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 catalyst of gram and investigates with embodiment 1, and the exhaust sampling analysis result is: methanol conversion 99.35%, monomethyl amine selectivity 22.32%, dimethylamine selectivity 31.65%, trimethylamine 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 boehmites and an amount of rare nitric acid, fully mediate agglomerating, extrusion, health are dried, make catalyst and investigation with embodiment 1, the sample analysis result is: methanol conversion 99.16%, monomethyl amine selectivity 21.37, dimethylamine selectivity 30.81, trimethylamine 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 potassium nitrate, 15 parts of 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%, monomethyl amine selectivity 22.36%, dimethylamine selectivity 31.47%, trimethylamine 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 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%, monomethyl amine selectivity 22.35% with embodiment 2, dimethylamine selectivity 30.87%, trimethylamine 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 catalyst with aforementioned method, the investigation result is: methanol conversion 99.36%, monomethyl amine selectivity 21.37%, dimethylamine selectivity 30.56%, trimethylamine 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 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%, monomethyl amine selectivity 22.80%, dimethylamine selectivity 30.72%, trimethylamine selectivity 46.48%.
[embodiment 8]
100 gram sodium type clinoptilolites (natural, SiO
2/ Al
2O
3Mol ratio=10) make catalyst by embodiment 6 method steps, get 2 these catalyst of gram and investigate 100 hours, the sample analysis result is: methanol conversion 98.66%, monomethyl amine selectivity 24.11%, dimethylamine selectivity 30.62%, trimethylamine 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 catalyst and investigation, the sample analysis result is: methanol conversion 99.23%, monomethyl amine selectivity 21.01%, dimethylamine selectivity 30.81%, trimethylamine 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 boehmites, 150 gram potassium nitrate, 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 catalyst in 3 hours.Take a morsel this catalyst grinds and sieves out 12～16 orders, gets 2 grams and investigates, and the result is: methanol conversion 98.90%, monomethyl amine selectivity 23.03%, dimethylamine selectivity 30.64%, trimethylamine selectivity 46.33%.
[embodiment 11]
Alumina component is transformed into each 25 kilograms of siliceous 35 weight % sial and boehmites among the embodiment 10, all the other are identical, investigate the result to be: methanol conversion 98.81%, monomethyl amine selectivity 25.71%, dimethylamine selectivity 30.82%, trimethylamine selectivity 43.47%.
[embodiment 12]
Do not add potassium nitrate among the embodiment 10, all the other together.The investigation result is: methanol conversion 98.87%, monomethyl amine selectivity 24.03%, dimethylamine selectivity 30.57%, trimethylamine 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%, monomethyl amine selectivity 24.88%, dimethylamine selectivity 30.65%, trimethylamine selectivity 44.47%.
[embodiment 14]
Remove magnesium acetate among the embodiment 10, all the other together.Investigate the result: methanol conversion 98.63%, monomethyl amine selectivity 25.62%, dimethylamine selectivity 30.78%, trimethylamine selectivity 43.60%.
[embodiment 15]
Remove potassium nitrate among the embodiment 10, add 300 gram calcium nitrate, all the other together.Investigate the result: methanol conversion 98.83%, monomethyl amine selectivity 23.0%, dimethylamine selectivity 30.75%, trimethylamine 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%, monomethyl amine selectivity 22.81%, dimethylamine selectivity 29.07%, trimethylamine 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 sodium nitrate and 0.5 part of calcium 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%, monomethyl amine selectivity 22.13%, dimethylamine selectivity 26.80%, trimethylamine selectivity 51.07%.
[comparative example 3]
4.5 parts in embodiment 1 gained molecular sieve and 25 parts of boehmites and an amount of rare nitric acid are mediated and are made catalyst, the same investigation, the result is: methanol conversion 98.43%, monomethyl amine selectivity 23.54%, dimethylamine selectivity 27.71%, trimethylamine selectivity 48.75%.
Claims (7)
1, a kind of be used for methyl alcohol and ammonia mutually amination produce the catalyst of methylamine, contain following component by weight percentage:
A) 5～40% crystal aluminosilicate;
B) 60～95% composite oxides of forming by aluminium oxide and silica, wherein in the composite oxides by weight percentage the amount of silica be 0.5～60%.
2, according to claim 1 described be used for methyl alcohol and ammonia mutually amination produce the catalyst of 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 modenite, ZSM-5, β zeolite or the clinoptilolite molecular sieve.
3, according to claim 1 described be used for methyl alcohol and ammonia mutually amination produce the catalyst of methylamine, it is characterized in that by weight percentage the consumption of the composite oxides be made up of aluminium oxide and silica is 70～85%.
4, according to claim 1 described be used for methyl alcohol and ammonia mutually amination produce the catalyst of methylamine, it is characterized in that in the composite oxides that the amount of silica is 5～30% by weight percentage.
5, according to claim 1 described be used for methyl alcohol and ammonia mutually amination produce the catalyst of methylamine, the pore volume that it is characterized in that composite oxides is 0.4～1.3 a milliliter/gram, specific area is 150～500 meters
2/ gram.
6, according to claim 5 described be used for methyl alcohol and ammonia mutually amination produce the catalyst of methylamine, the pore volume that it is characterized in that composite oxides is 0.5～1.0 a milliliter/gram, specific area is 200～400 meters
2/ gram.
7, according to claim 6 described be used for methyl alcohol and ammonia mutually amination produce the catalyst of methylamine, it is characterized in that also containing in the catalyst at least a in the compound that is selected from alkali metal, alkaline-earth metal, rare earth metal or phosphorus, its consumption is 0.001～5% by weight percentage.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426488A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methylamine by amination of methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4217240A (en) * | 1976-09-02 | 1980-08-12 | E. I. Du Pont De Nemours And Company | Stable aluminosilicate aquasols having uniform size particles and their preparation |
| JPS57169445A (en) * | 1981-04-10 | 1982-10-19 | Nitto Chem Ind Co Ltd | Preparation of methylamine |
| US4398041A (en) * | 1982-01-29 | 1983-08-09 | Air Products And Chemicals, Inc. | Process for manufacturing alkylamines |
| JPS59227841A (en) * | 1983-06-08 | 1984-12-21 | Nitto Chem Ind Co Ltd | Selective production of dimethylamine |
| CN1084220C (en) * | 1998-09-16 | 2002-05-08 | 中国石油化工总公司 | Catalyst and technological process for methylamine production with methanol or dimethyl ether and ammonia |
| CN1177801C (en) * | 2000-09-29 | 2004-12-01 | 中国石油化工股份有限公司 | Methylamine catalyst and preparation process thereof |
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2003
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Cited By (1)
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| CN114426488A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methylamine by amination of methanol |
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