CN1151984A - Catalyst for ammoniation reaction - Google Patents
Catalyst for ammoniation reaction Download PDFInfo
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- CN1151984A CN1151984A CN 95117838 CN95117838A CN1151984A CN 1151984 A CN1151984 A CN 1151984A CN 95117838 CN95117838 CN 95117838 CN 95117838 A CN95117838 A CN 95117838A CN 1151984 A CN1151984 A CN 1151984A
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- Prior art keywords
- catalyzer
- reaction
- carrier
- catalyst
- active ingredient
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims 2
- 229910003962 NiZn Inorganic materials 0.000 claims 2
- 238000012216 screening Methods 0.000 claims 2
- 150000001412 amines Chemical class 0.000 abstract description 10
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000005913 hydroamination reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 53
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 17
- 230000009466 transformation Effects 0.000 description 11
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 4
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 4
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical group CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZHCKPJGJQOPTLB-UHFFFAOYSA-N 1-methyl-4-imidazoleacetic acid Chemical compound CN1C=NC(CC(O)=O)=C1 ZHCKPJGJQOPTLB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910003322 NiCu Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical group CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical group CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- SPVVMXMTSODFPU-UHFFFAOYSA-N 3-methyl-n-(3-methylbutyl)butan-1-amine Chemical group CC(C)CCNCCC(C)C SPVVMXMTSODFPU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical group CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine group Chemical group C(CCC)N(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical group CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An ammoniation reaction catalyst is prepared from carrier (Ni, Zn, Fe, etc) as active components (Ni: Zn: 1: 0.01-0.5) and carrier (rest: 1: 0-0.1). The catalyst is prepared by any one of a precipitation method, a coprecipitation method and an impregnation method. The catalyst can be applied to various ammoniation reactions and can be used for preparing C2-C5 fatty amine. The proportion of mono-, di-and triamines in the product can be varied within wide limits according to requirements. The catalyst can be used for carrying out the hydroamination reaction at normal pressure and low temperature, and the preparation of the catalyst is simple.
Description
The present invention relates to a kind of aminating reaction catalyst, specifically, relate to a kind of Fatty Alcohol(C12-C14 and C12-C18) and corresponding aldehyde, ketone about C2～C5, in the presence of ammonia and hydrogen, the synthetic used catalyzer of amine.
In chemical industry, amine-containing compound all will be used in many fields, comprises monoamine, diamine and triamine compound, and these compounds are often prepared by the hydrogen aminating reaction by alcohol, ketone or aldehyde and ammonia and hydrogen, hydrogen aminating reaction mechanism can be divided into for three steps: the first step, and the raw alcohol dehydrogenation generates aldehydes or ketones; In second step, aldehydes or ketones and ammonia addition generate imines; In the 3rd step, the further hydrogenation of imines generates amine.Above-mentioned hydrogen aminating reaction must just can carry out in the presence of catalyzer.
U.S. Pat 2,363,721 provide a kind of compound of nickel and aluminium that uses to be catalyzer, carry out the method for the synthetic amine of gas-solid catalysis by alcohol and ammonia, hydrogen, but because contain primary in the final product, the second month in a season and three kinds of amine of uncle and reaction intermediate nitrile and unreacted alcohol, so product separation is refining very difficult.
Chinese patent CN1,057,831A has reported a kind of method by carbon two-carbon 9 fatty alcohol system aliphatic amide, and this method for preparing amine divides two sections to carry out, and the typical scenario of first section employed catalyzer is Cu
1.5O
3, the typical scenario of second section used catalyzer is CuZnSi
7.5O
8.5, this method for preparing amine has higher selectivity and transformation efficiency, but owing to adopted two-stage method, operational path is long, needs bigger facility investment, and it is more to prepare the step of the catalyzer that is used for this method, makes can be subjected to more multifactor influence in the preparation process.
Chinese patent CN1,031,663A has reported with Ni, Cu, Cr and has loaded on Al
2O
3On aminating reaction catalyst, carrier is α-Al
2O
3Or θ-Al
2O
3Or both are with the mixture of arbitrary proportion composition, be to get in 750～920 ℃ of roastings 2～8 hours by boehmite, wherein the weight percentage of carrier is 65-90%, other are active ingredient, each active ingredient is respectively NiCu=1 with the atomic ratio measuring to Ni: 0.2-0.8, NiCr=1: 0-0.5, NiRe=1: 0.001-0.01.This catalyzer also can be made the mixture of Ni, Cu, Cr, Ti by the precipitator method; Al wherein
2O
3Be γ-phase, the weight percent in catalyzer is 63-32%, and the rest activity component is 37-68, and each active ingredient is respectively NiCu=1 with the atomic ratio measuring to Ni: 1.0-2.0, NiCr=1: 0.1-0.5, NiTi=1: 1.0-2.0.This catalyzed reaction is carried out under 5-60atm (preferably 15-45atm) and 160-300 ℃, and trickle bed is adopted in reaction, and this catalyzer can be used for multiple aminating reaction, but owing to adopted high pressure, need to use pressure-resistant equipment, invest bigger, and operation is comparatively complicated, and certain danger is arranged.
Purpose of the present invention is exactly in order to overcome the shortcoming of above-mentioned prior art, to obtain a kind of improved catalyzer that is used for aminating reaction.
The inventor is through long term studies, a kind of improved aminating reaction catalyst is proposed, by carrier loaded metal or its oxide compounds such as Ni, Fe, Zn gone up, carrier shared weight ratio in catalyzer is 30～70%, surplus is active ingredient, each active ingredient is respectively Ni to the atomic ratio of N: Zn=1: 0.05～1: 0.5, and Ni: Fe=1: 0.0～1: 0.1.
Described carrier is prepared by following method:
(1) add hydrochloric acid soln at the water glass solution of 5-25wt%, the weight percent concentration 3.7～37wt% of hydrochloric acid soln, temperature of reaction is controlled at 0～50 ℃, when PH=3～6, stops to add hydrochloric acid soln;
(2) with the gel of step (1) gained with the deionized water washing after, with gel pulp in 5～15% bicarbonate of ammonia or sal volatile, wash to the Na ion content less than 0.1%, filter;
(3) will filter thing 100～250 ℃ of dryings, obtain pulverulent solids, sieve to such an extent that 55～70 purposes usefulness is the carrier of catalyzer.
The carrier of catalyzer among the present invention also can be selected commercially available silica gel, diatomite, silicon-dioxide for use, or above the two carrier with arbitrary proportion mixing gained.
The atomic ratio of above-mentioned activity of such catalysts component is for being preferably Ni: Zn=1: 0.1-1: 0.2, and Ni: Fe=1: 0.05-1: 0.1.
The specific surface area of above-mentioned catalyzer is 50～150m
2/ g, tap density is 1.05～1.20g/ml, granularity is 55～70 orders.
Above-mentioned Preparation of catalysts method is: active ingredient is any with the aqueous solution of its corresponding salt or alcoholic solution, any by the precipitator method or coprecipitation method or pickling process, load on the described carrier, drying, impact briquetting, 200～600 ℃ after with hydrogen reducing the catalyzer finished product.
Wherein the precipitator method or coprecipitation method are: take by weighing a certain amount of nickel, zinc, molysite, as alkoxide, vitriol, nitrate etc., be preferably nitrate or alkoxide.Be made into the alcoholic solution or the aqueous solution of 10～50wt%.The carrier that adding makes by aforesaid method, limit stir, the limit drip concentration be 1～10% basic solution as precipitation agent, its basic solution can be Na
2CO
3, NH
4OH, NaOH, KOH a kind of or their mixture.After precipitation is finished, aging 10～20 hours, with the deionized water washing, 100～300 ℃ of dryings, impact briquetting under certain pressure, 200～600 ℃ after with hydrogen reducing the catalyzer finished product.
In addition, the load of active ingredient also can be undertaken by the mode that branch soaks or soaks altogether, dry method and wet method can, dipping solution can be that the aqueous solution or the alcoholic solution of the corresponding salt of active ingredient is any.
Catalyzer of the present invention can be applied in all kinds of aminating reactions, is suitable for especially by C2～C5 alcohol and corresponding aldehyde, ketone, and in the presence of ammonia and hydrogen, producing general formula is R
nNH
3-nAliphatic amide, wherein R is C2～C5, n is 1～3.
The method that catalyzer of the present invention is used to produce above-mentioned amine compound is: under normal pressure or pressurization and 100～200 ℃, with C2～C5 Fatty Alcohol(C12-C14 and C12-C18) or corresponding aldehydes or ketones, NH
3, H
2Join continuously in the fixed-bed catalytic reactor, keep alcohol (aldehydes or ketones] the charging air speed be 0.05～0.50hr
-1, alcohol: NH
3: H
2Material molar ratio be 1: 1～5: 1～5, produce above-mentioned amine compound according to the fixed bed reaction mode.
Compared with prior art, the present invention has the following advantages:
(1) catalyzer of the present invention can carry out aminating reaction under normal pressure and lesser temps (100-200 ℃), do not need pressure-resistant equipment.
(2) catalyzer of the present invention is finished one step of aminating reaction, and is simple to operate.
(3) catalyzer of the present invention has advantages of high catalytic activity, and for example, in the reaction by ethanol preparation ethamine, ethanol conversion is greater than 97%.
(4) catalyzer of the present invention has good selectivity, and for example, distribution single, double, triamine can be regulated with the need, the growing amount of impurity product such as nitrile, alkane seldom, the separation of purpose product is easy.
(5) catalyzer of the present invention is used for aminating reaction, has improved the efficient of production process, has reduced production cost, can be widely used in the aminating reaction.
Embodiment
Embodiment 1
1). the preparation of carrier
In beaker, add and contain silica 1 0%, the sodium silicate solution 100ml of PH=12, add 15% hydrochloric acid soln 40ml with the rate of addition of 20ml/min, control reaction temperature is 20-35 ℃, leaves standstill 2 hours, filter, washing with gel pulp in 10% sal volatile, is washed with water to sodium ions content less than 0.1% after-filtration, and sieve after 6 hours 120 ℃ of bakings, fineness be a 55-70 purpose support of the catalyst.
2). the preparation of catalyzer finished product
In beaker, add 69g nickelous nitrate crystal, 5g zinc nitrate crystal, and add the 30ml water dissolution, and add carrier 7.5g while stirring with method for preparing, add 10% NH
3The aqueous solution, the control precipitation temperature is at 0～70 ℃, pH value is controlled at 6～9, leaves standstill 20 hours, filter, washing, 300 ℃ dry down, after the impact briquetting, with getting the catalyzer finished product behind 200～600 ℃ the hydrogen reducing, catalyzer composed as follows at last:
SiO
2?47wt％
Ni????45wt％
Zn????7wt％
Fe????1wt％
The evaluating catalyst test:
The 10ml catalyzer is packed in the fixed-bed reactor, and reaction conditions is as follows:
180 ℃ of temperature of reaction, reaction pressure are normal pressure, ethanol: ammonia: hydrogen=1: 3: 3 (mol ratio), ethanol air speed 0.24hr
-1, activity, the selectivity of continuous 100 hours evaluate catalysts.The reactor that the evaluation test of catalyzer is adopted is: Φ 20 * 400mm material is a stainless steel, and reactor is divided into upper and lower two sections.Epimere is that preheating section, hypomere are conversion zone.There is a thermowell centre, thermocouple measurement preheating and temperature of reaction, and preheating section also simultaneously as the mixing tank of ethanol with hydrogen, ammonia, can determine as required at every turn by the consumption of test catalyst.The activity of 24 hours evaluate catalysts of non-stop run in reactor, selectivity.Reaction product is divided 3420 gas chromatographic analysiss with north.But the content of single, double in the assay products, triamine and water, alcohol.Peak area quantification, appearance time are qualitative, calculate each component concentration with normalization method.
Its result is as follows:
In the table: MEA represents monoethylamine
| Test period | Transformation efficiency | Yield (%) | ||
| ????(hr) | ????(％) | ????MEA | ????DEA | ????TEA |
| ????4 | ????94.5 | ????19.2 | ????63.2 | ????12.1 |
| ????10 | ????96.5 | ????15.9 | ????61.6 | ????19.0 |
| ????20 | ????95.5 | ????16.6 | ????63.3 | ????15.6 |
| ????50 | ????92.2 | ????13.2 | ????58.0 | ????20.9 |
| ????100 | ????93.4 | ????13.2 | ????57.1 | ????23.1 |
DEA represents diethylamine
TEA represents triethylamine embodiment 21). Preparation of catalysts:
With embodiment 1
2). the evaluating catalyst experiment
Method is with embodiment 1., and test conditions changes into: 180 ℃ of temperature of reaction, reaction pressure are 200mmH
2O, 24 hours reaction times, ethanol air speed 0.24hr
-1, change ethanol: ammonia: the mol ratio of hydrogen, its result such as following table:
| Ethanol: ammonia: hydrogen | Transformation efficiency | Yield (%) | ||
| (mol ratio) | ????(％) | ????MEA | ????DEA | ????TEA |
| ????1∶3∶6 | ????95.5 | ????15.8 | ????70.5 | ????9.2 |
| ????1∶4∶2 | ????97.7 | ????16.2 | ????58.8 | ????22.7 |
| ????1∶3∶3 | ????96.3 | ????15.7 | ????61.2 | ????19.4 |
Embodiment 3
1). Preparation of catalysts:
With embodiment 1
2). the evaluating catalyst experiment
Method is with embodiment 1., and the loadings of catalyzer is 10ml, and replacing ethanol with n-propyl alcohol is raw material, successive reaction 24 hours, and its result such as following table:
| Temperature ℃ | The pressure gauge pressure | Alcohol air speed hr -1 | Alcohol: hydrogen: ammonia (mol) | Transformation efficiency % | Yield % (mol) | |||
| ????MNPA | ????DNPA | ????TNPA | ????C1 | |||||
| ????170 | ????1.0 | ????0.096 | ????1∶1∶1 | ????92.5 | ????7.85 | ????53.2 | ????30.5 | ????0.5 |
| ????190 | ????1.0 | ????0.096 | ????1∶1∶1 | ????99.2 | ????13.3 | ????52.4 | ????27.5 | ????3.3 |
| ????180 | ????1.0 | ????0.096 | ????1∶4∶1 | ????98.0 | ????7.99 | ????55.5 | ????28.7 | ????2.67 |
| ????180 | ????1.0 | ????0.050 | ????1∶1∶1 | ????99.3 | ????9.80 | ????57.8 | ????26.3 | ????2.58 |
| ????180 | ????5.0 | ????0.096 | ????1∶1∶1 | ????96.7 | ????10.4 | ????55.5 | ????29.3 | ????1.76 |
In the table: MNPA represents a just interior amine
DNPA represents di-n-propylamine
TNPA represents Tri-n-Propylamine
C1 represents methane
Embodiment 4
1) Preparation of catalysts:
With embodiment 1
2) evaluation experimental of catalyzer
Method is with embodiment 1., and the loadings of catalyzer is 10ml, and replacing ethanol with Virahol is raw material, successive reaction 24 hours, and its result such as following table:
| Temperature ℃ | Pressure mmH 2O | Alcohol air speed hr -1 | Alcohol: hydrogen: ammonia (mol) | Transformation efficiency % | Yield % (mol) | |
| ??MIPA | ??DIPA | |||||
| ?160 | ??200 | ??0.24 | ??1∶3∶3 | ??95.0 | ??46.3 | ??49.1 |
In the table: MIPA represents monoisopropylamine
DIPA represents Diisopropylamine
Embodiment 5
1) Preparation of catalysts:
With embodiment 1
2) evaluating catalyst experiment
Method is with embodiment 1., and the loadings of catalyzer is 10ml, and replacing ethanol with propyl carbinol is raw material, successive reaction 24 hours, and its result such as following table:
MBA represents monobutylamine (MBA) in the table
| Temperature ℃ | Pressure mmH 2O | Alcohol air speed hr -1 | Alcohol: hydrogen: ammonia (mol) | Transformation efficiency % | Yield % (mol) | ||
| ????MBA | ???DBA | ???TBA | |||||
| ??190 | ???400 | ???0.15 | ??1∶3∶3 | ??94.3 | ????16.3 | ???69.1 | ???8.90 |
DBA represents dibutylamine
TBA represents Tributylamine
Embodiment 6
1) Preparation of catalysts:
With embodiment 1
2) evaluating catalyst experiment
Method is with embodiment 1., and the loadings of catalyzer is 10ml, and replacing ethanol with primary isoamyl alcohol is raw material, successive reaction 24 hours, and its result such as following table:
| Temperature ℃ | Pressure mmH 2O | Alcohol air speed hr -1 | Alcohol: hydrogen: ammonia (mol) | Transformation efficiency % | Yield % (mol) | |
| ??MIAA | ???DIAA | |||||
| ?170 | ???200 | ???0.22 | ???1∶3∶3 | ??96.3 | ???27.2 | ???69.1 |
In the table: MIAA represents an isobutylcarbylamine
DIAA represents di-iso-amylamine
Embodiment 7
1) Preparation of catalysts:
With embodiment 1
2) evaluation experimental of catalyzer
Method is with embodiment 1., and the loadings of catalyzer is 10ml, and replacing ethanol with acetone is raw material, successive reaction 24 hours, and its result such as following table:
In the table: MIPA represents monoisopropylamine
| Temperature ℃ | Pressure mmH 2O | Alcohol air speed hr -1 | Alcohol: hydrogen: ammonia (mol) | Transformation efficiency % | Yield % (mol) | |
| ??MIPA | ??DIPA | |||||
| ??150 | ???200 | ???0.48 | ???1∶3∶3 | ??98.0 | ??48.9 | ??49.1 |
DIPA represents two different interior amine embodiment 8
1) Preparation of catalysts:
With embodiment 1
2) evaluation experimental of catalyzer
Method is with embodiment 1., and the loadings of catalyzer is 10ml, under the condition of different pressures, and successive reaction 24 hours, its result such as following table:
| Temperature ℃ | Pressure MPa | Alcohol air speed hr -1 | Alcohol: hydrogen: ammonia (mol) | Transformation efficiency % | Yield % (mol) | ||
| ????MEA | ????DEA | ????TEA | |||||
| ???180 | Normal pressure | ????0.24 | ??1∶3∶3 | ????93.9 | ????21.8 | ????59.7 | ????12.4 |
| ???180 | ????0.5 | ????0.24 | ??1∶3∶3 | ????94.8 | ????28.0 | ????62.3 | ????4.44 |
| ???180 | ????1.2 | ????0.24 | ??1∶3∶3 | ????94.9 | ????30.6 | ????60.3 | ????3.9 |
When in industrial installation, producing ethamine, when using catalyzer of the present invention, generally be to carry out under pressurized operation, pressurized operation mainly is based on the back still-process and considers, system pressurization can make the ethamine still-process stride across the azeotropic district of ethamine-water, and pressurization is favourable to gas solid catalytic reaction.
Comparative example 1
1) Preparation of catalysts:
Change the self-control silica supports into alumina carrier (powdery, 60-100 order, rate of moisture absorption are 40%) that Shandong Aluminum Plant produces, consumption and Preparation of catalysts method be with embodiment 1., the catalyzer that makes through chemical analysis as can be known its nickel content be 45%.
2) evaluating catalyst experiment
Method is with embodiment 1., and the loadings of catalyzer is 10ml, and reactant feed is an ethanol, and its result such as following table were carried out in reaction 2 hours:
| Temperature ℃ | Pressure mmH 2O | Alcohol air speed hr -1 | Alcohol: hydrogen: ammonia (mol) | Transformation efficiency % | Yield % (mol) | |||
| ????MEA | ????DEA | ????TEA | ?????CA | |||||
| ???180 | ????150 | ????0.24 | ???1∶3∶3 | ???50.0 | ????12.5 | ????30.3 | ????5.47 | ?????1.48 |
In the table: MEA represents monoethylamine
DEA represents diethylamine
TEA represents triethylamine
CA represents acetonitrile
Comparative example 2
1) the neat preparation of catalysis
Solid support material: aluminium sesquioxide bead (diameter is 5-7mm, and Shandong Aluminum Plant produces) preparation method: adopt the equivalent impregnation method, now state as follows:
In a beaker, add 90g alumina carrier (water-intake rate is 40%), in another beaker, add 6 nitric hydrate nickel crystal 4 9.5g, and add the 17.6g dissolved in distilled water.Then carrier being poured into the nickel nitrate solution for preparing flooded 10 minutes, filter a small amount of excessive solution, the baking oven of putting into 120 ℃ is dried bead, in 550 ℃ of roasting 2～4hr, carry out reduction reaction at 450 ℃ of logical hydrogen, obtain catalyzer Hu Chengpin, know that through chemical analysis the nickel content in the catalyzer is 10%.
2) evaluating catalyst experiment
Method is with embodiment 1, and the loadings of catalyzer is 10ml, and reaction raw materials is an ethanol, and its result such as following table were carried out in reaction 2 hours:
In the table: MEA represents monoethylamine
| Temperature ℃ | Pressure mmH 2O | Alcohol air speed hr -1 | Alcohol: hydrogen: ammonia (mol) | Transformation efficiency % | Yield % (mol) | |||
| ?????MEA | ????DEA | ????TEA | ???CA | |||||
| ???180 | ????150 | ???0.24 | ??1∶3∶3 | ????67.5 | ?????13.1 | ????40.7 | ????11.8 | ???0.50 |
DEA represents diethylamine
TEA represents triethylamine
CA represents acetonitrile
Claims (7)
1. aminating reaction catalyst, be metal or its oxide compounds such as load Ni, Fe, Zn on carrier, it is characterized in that, carrier shared weight ratio in catalyzer is 30～70%, all the other are active ingredient, each active ingredient is respectively NiZn=1 to the atomic ratio of Ni: 0.05～1: 0.5, and NiFe=1: 0.0～1: 0.1;
Described carrier is prepared by following method:
(1) with water glass solution and the hydrochloric acid soln reaction of 5-25wt%, temperature of reaction is controlled at 0～50 ℃, PH=3～6;
(2) with the pulp in 5～15% bicarbonate of ammonia or sal volatile of the gel of step (1) gained, filter;
(3) will filter the thing drying, screening obtains carrier.
2. catalyzer according to claim 1 is characterized in that, the atomic ratio of described active ingredient is NiZn=1: 0.1～1: 0.2, and NiFe=1: 0.05～1: 0.1.
3. catalyzer according to claim 1 is characterized in that, the specific surface area of described catalyzer is 50～150m
2/ g, tap density is 1.05～1.20g/ml, granularity is 55～70 orders.
4. catalyzer according to claim 1 is characterized in that the preparation method of described carrier comprises the steps:
(1) with water glass solution and the hydrochloric acid soln reaction of 5-25wt%, temperature of reaction is controlled at 0～50 ℃, PH=3～6;
(2) with the pulp in 5～15% bicarbonate of ammonia or sal volatile of the gel of step (1) gained, filter;
(3) will filter the thing drying, screening obtains carrier.
5. according to claim 1 or 4 described catalyzer, it is characterized in that the weight percent concentration 3.7～37wt% of described hydrochloric acid soln.
6. the described Preparation of catalysts method of claim 1, it is characterized in that, active ingredient is any with the aqueous solution of its corresponding salt or alcoholic solution, any by the precipitator method or coprecipitation method or pickling process, load on the described carrier, drying, impact briquetting, 200～600 ℃ after with hydrogen reducing the catalyzer finished product.
7. catalyzer according to claim 1 is characterized in that, it is R that described catalyzer can be used for producing general formula
nNH
3-nAliphatic amide, wherein R is C2～C5, n is 1～3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117838A CN1047960C (en) | 1995-12-15 | 1995-12-15 | Catalyst for ammoniation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117838A CN1047960C (en) | 1995-12-15 | 1995-12-15 | Catalyst for ammoniation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1151984A true CN1151984A (en) | 1997-06-18 |
| CN1047960C CN1047960C (en) | 2000-01-05 |
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ID=5081385
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95117838A Expired - Fee Related CN1047960C (en) | 1995-12-15 | 1995-12-15 | Catalyst for ammoniation reaction |
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| CN (1) | CN1047960C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498834A (en) * | 2014-09-26 | 2016-04-20 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst and application of heterogeneous catalyst in ammoniation reaction of polyhydroxy compound |
| CN107915645A (en) * | 2017-10-12 | 2018-04-17 | 浙江晋巨化工有限公司 | A kind of n-butylamine production method |
| CN111097421A (en) * | 2018-10-29 | 2020-05-05 | 中国科学院大连化学物理研究所 | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same |
| CN112691668A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Catalyst for producing ethylamine and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1010284B (en) * | 1987-08-29 | 1990-11-07 | 中国石油化工总公司石油化工科学研究院 | Catalyst for ammoniation |
| CN1025732C (en) * | 1990-06-30 | 1994-08-24 | 中国石油化工总公司上海石油化工总厂 | Method of preparing aliphatic amine from C2-C9 fatty alcohol |
| CN1101629A (en) * | 1994-07-27 | 1995-04-19 | 华南理工大学 | Calicining cement technology by adding rare earth poor ore or rare earth waste slag |
-
1995
- 1995-12-15 CN CN95117838A patent/CN1047960C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498834A (en) * | 2014-09-26 | 2016-04-20 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst and application of heterogeneous catalyst in ammoniation reaction of polyhydroxy compound |
| CN105498834B (en) * | 2014-09-26 | 2017-11-10 | 中国科学院大连化学物理研究所 | A kind of heterogeneous catalyst and its application in polyol aminating reaction |
| CN107915645A (en) * | 2017-10-12 | 2018-04-17 | 浙江晋巨化工有限公司 | A kind of n-butylamine production method |
| CN111097421A (en) * | 2018-10-29 | 2020-05-05 | 中国科学院大连化学物理研究所 | Supported metal catalyst and method for preparing primary amine by catalyzing aldehyde compound by using same |
| CN112691668A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Catalyst for producing ethylamine and preparation method and application thereof |
| CN112691668B (en) * | 2019-10-23 | 2023-12-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylamine and preparation method and application thereof |
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|---|---|
| CN1047960C (en) | 2000-01-05 |
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