CN102151571B - Catalyst for synthesizing ethylene diamine via dichloroethane method, preparation method thereof and method for synthesizing ethylene diamine by using same - Google Patents
Catalyst for synthesizing ethylene diamine via dichloroethane method, preparation method thereof and method for synthesizing ethylene diamine by using same Download PDFInfo
- Publication number
- CN102151571B CN102151571B CN 201110040741 CN201110040741A CN102151571B CN 102151571 B CN102151571 B CN 102151571B CN 201110040741 CN201110040741 CN 201110040741 CN 201110040741 A CN201110040741 A CN 201110040741A CN 102151571 B CN102151571 B CN 102151571B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal
- ethylenediamine
- reaction
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 62
- 239000002184 metal Substances 0.000 claims abstract description 62
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000000470 constituent Substances 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000001556 precipitation Methods 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 235000010981 methylcellulose Nutrition 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000001246 colloidal dispersion Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000005243 fluidization Methods 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 210000002966 serum Anatomy 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012224 working solution Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 7
- 230000035484 reaction time Effects 0.000 abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910002482 Cu–Ni Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 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 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 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
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- -1 transition metal Co Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst, a preparation method thereof and application of the catalyst in the synthesis of ethylene diamine via a dichloroethane method. The active components of the catalysts comprise three to four metals which occupy 35-45% of the total weight of the catalyst; the other components comprise oxygen and skeleton silica, which are matched with the metals in the active components; the basic constituents in the active components comprise Co and a lanthanum metal; the Co occupies 75-85% of the total weight of the active components of the catalyst; and the lanthanum metal occupies 8-10% of the total weight of the active components of the catalyst. In the invention, the catalyst is applied to the synthesis of ethylene diamine via the dichloroethane method for the first time; by means of the using of the catalyst, the mole ratio of the ammonia and the dichloroethane is effectively reduced; and by using low-concentration ammonia water, high-yield ethylene diamine can be selectively produced, wherein the mole ratio of the ammonia to the dichloroethane is reduced to 1.2-2.6: 1 and the ammoniation reaction time is shortened to 60% of the ammoniation reaction time in the prior art.
Description
Technical field
The invention belongs to catalyst field, especially a kind of for the Catalysts and its preparation method of dichloroethane law synthesis of ethylenediamine and the method for using this catalyst synthesis of ethylenediamine.
Background technology
Ethylenediamine is important chemical intermediate, and the method for producing ethylenediamine both at home and abroad mainly comprises dichloroethane law and Girbotal process, and wherein the production technology of dichloroethane law accounts for about 58% of overall process route, and Girbotal process accounts for 42%.BASF at first succeeds in developing Girbotal process, thereafter more American-European company adopts, adopt the metallic catalysts such as Ni, Co, Cu, 150～230 ℃ of reaction temperatures, reaction pressure 20.0～30.0MPa, the main products such as ethylenediamine and piperazine that generate of reaction, when wherein the dichloroethanes conversion ratio was 60-80%, the classical group of product became to be distributed as ethylenediamine 71-80%.The technique of domestic monoethanolamine production is: 210-350 ℃, 17-24MPa, liquid air speed 2.7h-1, ammonia and monoethanolamine ratio are under 5.9 conditions, the conversion ratio of monoethanolamine can reach 86%, ethylenediamine and piperazine selectively be respectively 42.3% and 33%, the monoethanolamine unit consumption is up to 1.78-1.85 ton/ton EDA.Because the Girbotal process product is single, and oil price is high at present, and the monoethanolamine price fluctuation is large (once reaching 24000 yuan/tons) again between 2007-2008, and the one-tenth that Girbotal process is produced ethylenediamine is higher.Therefore, what recent domestic was developed Ni-Re, Ni-Ti, Ni-Ru or other modified with noble metals in succession takes off (adding) hydrogen amination catalyst, improving the selective of ethylenediamine, as uses Co-Ni-Cu/Al
2O
3Be catalyst, the monoethanolamine conversion ratio is 76.9%, and the ethylenediamine yield is 49.7%.The United States Patent (USP) report adopts Cu-Ni as catalyst monoethanolamine aminating reaction, and wherein low Cu/Ni ratio is conducive to generate ethylenediamine, and high Cu-Ni ratio is conducive to generate diethylenetriamine.Japan Patent report adopts ultra-fine Ni Energy Deposition to improve reactivity at catalyst preparation process, and more domestic research report about the Girbotal process synthesis of ethylenediamine is also more, but many because of the former of catalyst performance thereby industrialization is not arranged always.
All about the uncatalysed processes that is of dichloroethane law synthesis of ethylenediamine technique, adopt in addition pipeline reactor to produce the method for ethylenediamine, and the method for dichloroethane law synthesis of ethylenediamine does not also have correlative study and report under catalytic action both at home and abroad.
Summary of the invention
The method that the object of the present invention is to provide a kind of Catalysts and its preparation method for the dichloroethane law synthesis of ethylenediamine and use this catalyst synthesis of ethylenediamine, the present invention has realized under catalyst action, reduces ammonia and dichloroethanes mol ratio or uses low concentration ammoniacal liquor can realize the high yield of ethylenediamine.
The present invention realizes that the technical scheme of purpose is as follows:
A kind of catalyst for the dichloroethane law synthesis of ethylenediamine, the active component of this catalyst is three to four kinds of metals, it is 35-45% that metal active constituent accounts for total catalyst weight percentage, all the other components are oxygen element and the framework silica that match with metal active constituent, the basis of described metal active constituent is Co and a kind of lanthanide series metal, Co accounts for the 75%-78% of metal active constituent gross weight, lanthanide series metal accounts for the 8%-10% of metal active constituent gross weight, supplementary element in the described metal active constituent is Mo, W, Ni, Sn, Ru, Pd, Pb, Bi, Fe, Mn, Ti, among the Zr one or both, when described supplementary element is metal Ru or Pd, its weight accounts for respectively the 0.28-3.0% of total catalyst weight, described supplementary element is Mo, W, Ni, Sn, Ru, Pd, Pb, Bi, Fe, Mn, during among Ti and the Zr two kinds, the content sum of two kinds of metal ingredients accounts for the 12-17% of catalyst activity component total amount, and the atomic ratio of two kinds of metals is 1: 1.
And described supplementary element is Mo, Ru, Pd, Bi, Fe or Zr preferably.
And the granularity of described catalyst is 700-800nm, total specific surface 380～430m
2/ g, pore volume 0.68～0.73mL/g.
A kind of method of the catalyst for the preparation of the dichloroethane law synthesis of ethylenediamine is characterized in that it may further comprise the steps:
(1) take by weighing respectively the soluble-salt of metal in the activity component metal oxide, be made into respectively the slaine working solution of molar content 0.008-0.015M, place recorder jar separately, configuration alkali precipitation agent solution places recorder jar;
(2) pure water is added in the retort, be heated to 97+2 ℃ under stirring, multiply and stream add 4 kinds of working metal liquid, stir 280-300 rev/min of revolution, the fully isoelectric point of precipitation according to slaine in the raw material slowly adds the alkali precipitation agent, the flow of control alkali precipitation agent, adopt echelon PH swinging method to realize the precipitation of metal, PH swings 5-8 time repeatedly, sour side PH ≈ 3.8, alkali side ≈ 10.3, reaction end PH ≈ 3.8-4.0, whole time 170-180 minute, simultaneously by adding water management colloidal dispersion solid content 0.5%-2.0%g/L, after reaction finishes, whole system 120-150 ℃ of crystallization 36 hours, is then regulated PH ≈ 7.8-8.0, crystallization 36 hours again under 120-150 ℃, filter, get filter cake, with filter cake with the pure water washing for several times, until wash water electrical conductivity ≯ 10 μ s/cm;
(3) qualified cake that obtains after step (2) washing is mixed by adding water with carrier silica, be adjusted to slurries, the control solid content 880-900 rev/min, pulp 55-60 minute, is regulated PH ≈ 4.8-6.0 at 1.0-5.0%;
(4) in above-mentioned mixed serum, add the binding agent methylated cellulose aqueous solution, guarantee that the weight final concentration of methylcellulose in system is 0.05-0.06%, dispersion tank is airtight, connect compressed air, control flow 60-100ml/min inputs slurries in the fluidisation reaction bed, through 600-650 ℃ of fluid bed fluidized state dehydration and oxidation, obtaining granularity is the 700-800nm grained catalyst
Described adhesive is selected from methylcellulose, hydroxylated cellulose or polyvinyl alcohol.
And described carrier is that silica is with the form adding of Ludox or silester.
And the soluble-salt of described metal is solubility nitrate or the soluble-salt hydrochlorate of metal or the solubility acetate of metal of metal, and wherein Mo, W are oxysalt.
And, described alkali precipitation agent be NaOH, sodium carbonate, hydroxide by or organic amine, wherein organic amine is triethylamine or n-butylamine.
A kind of method of applications catalyst catalysis dichloroethanes synthesis of ethylenediamine is characterized in that it may further comprise the steps:
(1) 1.15%～5.68% ratio that adds the dichloroethanes raw material weight in reaction accurately take by weighing catalyst and add in circulate in the reactor, closed reactor adds water, use inert gas replacement, be heated to 180-190 ℃ under the stirring after, pass into H
2+ N
2Gaseous mixture, control system pressure is no more than 0.6Mpa, reacts after 160-200 minute, is cooled to room temperature;
(2) add liquefied ammonia, make ammonia concn 35% in the reactor, be heated to 90-100 ℃;
(3) add dichloroethanes, so that liquefied ammonia/dichloroethanes molecular proportion 1.2～2.6: 1,98-108 ℃ of control reaction temperature treats that dichloroethanes adds complete, and 108 ± 2 ℃ of control temperature of reaction system were kept 15-25 minute, and course of reaction is namely finished in cooling.
Advantage of the present invention and good effect are:
1, the present invention's applications catalyst in the dichloroethane law synthesis of ethylenediamine first, the use of this catalyst effectively reduces the mol ratio of ammonia and dichloroethanes reaction, use low concentration ammoniacal liquor optionally to produce the ethylenediamine of high yield, wherein the mol ratio of ammonia and dichloroethanes mol ratio drops to 1.2～2.6: 1, reaction temperature has dropped to 98～130 ℃, the aminating reaction time shorten is 60% of existing technique, and the recyclable regeneration of catalyst.
2, can be by adding catalyst selectivity ground control distribution of reaction products among the present invention, the dichloroethanes synthesis of ethylenediamine is selectively greater than 70%, many support amine reaction overall selectivitys 97%～98%, dichloroethanes conversion ratio 99.5%～100%, the poly-multi-enamine high-boiling components of generation is less than 0.5%.
3, the raw material of catalyst of the present invention comprises in the transition metal such as transition metal Co, Mo, W, Ni, Sn, Ru, Pd, Bi, Fe, Mn, Ti, Zr, La system several, the raw material range of choice is extensive, the preparation method is simple, synthetic catalyst type is more, wherein powder catalyst particle mean size is 700～800nm, and total specific surface is up to 360～430m
2/ g, pore volume 0.68～0.73mL/g has guaranteed the good catalytic performance of this catalyst.
The specific embodiment
Below in conjunction with embodiment, the present invention will be further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The catalyst of the present invention's preparation is comprised of active component and silica, active component is three to four kinds of metals, it is 35-45% that active component accounts for total catalyst weight percentage, all the other components for active component in the metal oxygen element and the framework silica that match, basis in the active component is Co and a kind of lanthanide series metal, Co accounts for the 75%-78% of catalyst activity component gross weight, lanthanide series metal accounts for the 8%-10% of catalyst activity component total amount, supplementary element in the active component is Mo, W, Ni, Sn, Ru, Pd, Pb, Bi, Fe, Mn, Ti, among the Zr one or both, when supplementary element is metal Ru or Pd, metal Ru or Pd account for total catalyst weight ratio 0.28-3.0%, described supplementary element is Mo, W, Ni, Sn, Ru, Pd, Pb, Bi, Fe, Mn, during among Ti and the Zr two kinds, the content sum of two kinds of metal ingredients accounts for the 12-17% of catalyst activity component total amount, and the atomic ratio of two kinds of metals is 1: 1.
What the present invention adopted is sol-gal process, form colloidal sol after will containing three to four kinds of metal soluble-salt solution and alkali precipitation agent reaction, sol particles diameter 70～90nm, add again framework silica and adhesive, through 600-650 ℃ of fluid bed fluidized state dehydration and oxidation (time), obtaining granularity is the 700-800nm grained catalyst, total specific surface 380～430m
2/ g, pore volume 0.68～0.73mL/g.
Wherein metal soluble-salt solution comprises Co (NO
3)
26H
2O, CoCl
26H
2O, Bi (NO
3)
35H
2O, Zr (NO
3)
45H
2O, ZrOCl
28H
2O, La (NO
3)
36H
2O, Ce (NO
3)
36H
2O, Na
2MoO
42H
2O, LaCl
37H
2O, LaCl
37H
2O, W (NO
3)
6, Ni (NO
3)
26H
2O, Ti (NO
3)
4, Fe (NO
3)
39H
2O, Mn (NO
3)
24H
2O, SnCl
45H
2O, RuCl
34H
2O, Pb (NO
3)
2, and other soluble-salts, be prior art, do not enumerate one by one, its combining form is various, also comprises following combination except the combination of following three enforcements: 1, Co (NO
3)
26H
2O, Mn (NO
3)
24H
2O, RuCl
34H
2O, Ce (NO
3)
36H
2O, 2, Co (NO
3)
26H
2O, Bi (NO
3)
35H
2O, W (NO
3)
6, La (NO
3)
36H
2O, 3, CoCl
26H
2O, SnCl
45H
2O, RuCl
34H
2O, LaCl
37H
2O, 4, Co (NO
3)
26H
2O, Fe (NO
3)
39H
2O, Mn (NO
3)
24H
2O, La (NO
3)
36H
2O, the weight ratio between composition gets final product referring to embodiment.
Embodiment 1
1, a kind of preparation method of the catalyst for the dichloroethane law synthesis of ethylenediamine, the step of method is as follows:
(1) configuration of working metal liquid: accurately take by weighing respectively cobalt nitrate (Co (NO3) 26H2O) 154.1 grams, bismuth nitrate (Bi (NO3) 35H2O) 7.76 grams, zirconium nitrate (molecular formula: Zr (NO3) 45H2O) 6.86 grams, lanthanum nitrate (La (NO3) 36H2O) 11.22 grams, being mixed with the concentration of amounting to metal is the 0.008M aqueous solution, be placed in separately the recorder jar, alkali precipitation agent configuration: the preparation percentage by weight is the aqueous solution of 8% sodium carbonate, places recorder jar;
Wherein the alkali precipitation agent is the finite concentration alkaline solution, can also be NaOH, hydroxide by, organic amine wherein organic amine such as triethylamine, n-butylamine etc.
(2) press the synthetic weight metering reactive group water of catalyst, measuring the 1000ml pure water adds in the retort, be heated to 97 ± 2 ℃ under stirring, multiply and stream add 4 kinds of working metal liquid, stir 280-300 rev/min of revolution, the fully isoelectric point of precipitation according to slaine in the raw material, slowly add the alkali precipitation agent, the flow of control alkali precipitation agent adopts echelon PH swinging method to realize the precipitation of metal, PH swings 5-8 time repeatedly, acid side PH ≈ 3.8, alkali side ≈ 10.3, reaction end PH ≈ 3.8-4.0, whole time 170-180 minute, simultaneously by adding water management colloidal dispersion solid content 0.5%-2.0%g/L, after reaction finishes, with whole system 120-150 ℃ of crystallization 36 hours, then regulate PH ≈ 7.8-8.0, crystallization 36 hours again under 120-150 ℃ is filtered, and gets filter cake, with filter cake with the pure water washing for several times, until wash water electrical conductivity ≯ 10 μ s/cm;
Wherein PH swings and relies on " alkali precipitation agent " to regulate the alkali side, adopts the method that stops the alkaline chemical precipitation agent to sour side timing.
(3) qualified cake that obtains after step (2) washing is mixed by adding water with carrier material ethyl silicate solution 215ml or 169ml Ludox, regulate slurry solid content at 1.0-5.0%g/L, 880-900 rev/min pulp 55-60 minute, regulate PH ≈ 4.8-6.0;
Wherein the source of carrier material silica can be Ludox and or silester, Ludox is the amorphous colloidal solution of a kind of faintly acid, dioxide-containing silica 25%-30%, proportion 1.15-1.19g/cm
3, silester is the faintly acid organic silicon sol, dioxide-containing silica 28%-30%, proportion 0.93-0.94g/cm
3, following examples are identical.
(4) in above-mentioned mixed serum, add the binding agent methylated cellulose aqueous solution, guarantee that the weight final concentration of methylcellulose in system is 0.05-0.06%, dispersion tank is airtight, connect compressed air, control flow 60-100ml/min inputs slurries in the fluidisation reaction bed, through 600-650 ℃ of fluid bed fluidized state dehydration and oxidation, time of contact 35-38mim, obtaining granularity is 700-80Onm grained catalyst CoO-Bi
2O
3-ZrO
2-La
2O
3/ SiO
2
Wherein adhesive is except using methylcellulose, the also a kind of replacement in available hydroxylated cellulose or the polyvinyl alcohol.
2, the method for the dichloroethanes synthesis of ethylenediamine under the effect of above-mentioned catalyst, step is as follows:
(1) accurately take by weighing above-mentioned grained catalyst in 1.15%～5.68% ratio of raw material dichloroethanes weight and add in circulate in the reactor, closed reactor, the pure water of adding accurate-metering with pressure is used inert gas replacement, after being heated to 185 ℃ under stirring, pass into (H
2+ N
2) gaseous mixture, control system pressure is no more than 0.6Mpa, reacts after 180 minutes, and logical cooling water temperature is to room temperature;
(2) liquefied ammonia of adding amount of calculation with pressure is heated to 95 ℃ so that the interior ammoniacal liquor final concentration of reactor is 35%;
(3) add slow dichloroethanes with high-pressure metering pump, so that liquefied ammonia/dichloroethanes molecular proportion 2.3,98-108 ℃ of control reaction temperature, treat that dichloroethanes adds complete, 108 ± 2 ℃ of control temperature of reaction system were kept approximately 20 minutes, course of reaction is namely finished in cooling, synthesizes to get ethylenediamine.
Embodiment 2
1, a kind of preparation method of the catalyst for the dichloroethane law synthesis of ethylenediamine, the step of method is as follows:
(1) configuration of working metal liquid: accurately take by weighing respectively cobalt nitrate (Co (NO
3)
26H
2O) 148.2 grams, sodium molybdate [Na
2MoO
42H
2O] 7.76 grams, zirconium nitrate (molecular formula: Zr (NO
3)
45H
2O) 13.73 grams, cerous nitrate (Ce (NO
3)
36H
2O) 11.15 grams, wherein 3 kinds of nitrate are mixed with respectively the approximately 0.008M aqueous solution of tenor, sodium molybdate is mixed with approximately 0.008M ammonia spirit of tenor with 3% ammoniacal liquor, be placed in separately the recorder jar, alkali precipitation agent configuration: the preparation percentage by weight is the aqueous solution of 8% sodium carbonate, places recorder jar;
(2) press the synthetic weight metering reactive group water of catalyst, measuring the 1000ml pure water adds in the retort, be heated to 97 ± 2 ℃ under stirring, multiply and stream add 4 kinds of working metal liquid, stir 280-300 rev/min of revolution, the fully isoelectric point of precipitation according to slaine in the raw material, slowly add the alkali precipitation agent, the flow of control alkali precipitation agent adopts echelon PH swinging method to realize the precipitation of metal, PH swings 5-8 time repeatedly, acid side PH ≈ 3.8, alkali side ≈ 10.3, reaction end PH ≈ 3.8-4.0, whole time 170-180 minute, simultaneously by adding water management colloidal dispersion solid content 0.5%-2.0%, after reaction finishes, with whole system 120-150 ℃ of crystallization 36 hours, then regulate PH ≈ 7.8-8.0, crystallization 36 hours again under 120-150 ℃ is filtered, and gets filter cake, with filter cake with the pure water washing for several times, until wash water electrical conductivity ≯ 10 μ s/cm;
(3) qualified cake that obtains after step (2) washing is mixed by adding water with carrier material Ludox 169ml or ethyl silicate solution 215ml, regulate slurry solid content at 1.0-5.0%, 880-900 rev/min pulp 55-60 minute, regulate PH ≈ 4.8-6.0 (conditioning agent);
(4) in above-mentioned mixed serum, add the binding agent methylated cellulose aqueous solution, guarantee that the weight final concentration of methylcellulose in system is 0.05-0.06%, dispersion tank is airtight, connect compressed air, control flow 60-100ml/min, slurries are inputted in the fluidisation reaction bed, and through 600-650 ℃ of fluid bed fluidized state dehydration and oxidation 35-38min, obtaining granularity is 700-800nm grained catalyst CoO-MoO-ZrO
2-Ce
2O
3/ SiO
2
2, the method for the dichloroethanes synthesis of ethylenediamine under the effect of above-mentioned catalyst, step is as follows:
(1) accurately taking by weighing above-mentioned grained catalyst in 1.15%～5.68% ratio of reacting processing industry dichloroethanes material weight also circulates in the reactor in the adding, closed reactor, the pure water of adding accurate-metering with pressure is used inert gas replacement, after being heated to 185 ℃ under stirring, pass into (H
2+ N
2) gaseous mixture, control system pressure is no more than 0.6Mpa, reacts after 180 minutes, and logical cooling water temperature is to room temperature;
(2) liquefied ammonia of adding amount of calculation with pressure is so that the interior ammonia concn 35% of reactor is heated to 95 ℃;
(3) add slow industrial dichloroethanes with high-pressure metering pump, so that liquefied ammonia/dichloroethanes molecular proportion 2.3,98-108 ℃ of control reaction temperature, treat that industrial dichloroethanes adds complete, 108 ± 2 ℃ of control temperature of reaction system were kept approximately 20 minutes, course of reaction is namely finished in cooling.
Embodiment 3
1, a kind of preparation method of the catalyst for the dichloroethane law synthesis of ethylenediamine, step is as follows:
(1) configuration of working metal liquid: accurately take by weighing respectively cobalt chloride (CoCl
26H
2O) 126.0 grams, palladium bichloride (PdCl
2) 0.41 gram, zirconium oxychloride (ZrOCl
28H
2O) 23.3 grams, lanthanum chloride (LaCl
37H
2O) 9.66 grams, palladium bichloride is mixed with 0.1M ammoniacal liquor and contains the approximately 0.002M aqueous solution of Pd, other 3 kinds of hydrochloric acid solutions are mixed with respectively the approximately 0.008M aqueous solution of tenor, and alkali precipitation agent configuration: accurately weighing sodium hydroxide is mixed with 5% the aqueous solution, places recorder jar;
(2) press the synthetic weight metering reactive group water of catalyst, measuring the 1000ml pure water adds in the retort, be heated to 97 ± 2 ℃ under stirring, multiply and stream add 4 kinds of working metal liquid, stir 280-300 rev/min of revolution, the fully isoelectric point of precipitation according to slaine in the raw material, slowly add the alkali precipitation agent, the flow of control alkali precipitation agent adopts echelon PH swinging method to realize the precipitation of metal, PH swings 5-8 time repeatedly, acid side PH ≈ 3.8, alkali side ≈ 10.3, reaction end PH ≈ 3.8-4.0, whole time 170-180 minute, simultaneously by adding water management colloidal dispersion solid content 0.5%-2.0%, after reaction finishes, with whole system 120-150 ℃ of crystallization 36 hours, then regulate PH ≈ 7.8-8.0, crystallization 36 hours again under 120-150 ℃ is filtered, and gets filter cake, with filter cake with the pure water washing for several times, until wash water electrical conductivity ≯ 10 μ s/cm;
(3) qualified cake that obtains after step (2) washing is mixed by adding water with carrier material Ludox 169ml or ethyl silicate solution 215ml, regulate slurry solid content at 1.0-5.0%, 880-900 rev/min pulp 55-60 minute, regulate PH ≈ 5.5-6.0;
(4) in above-mentioned mixed serum, add the binding agent methylated cellulose aqueous solution, guarantee that the weight final concentration of methylcellulose in system is 0.05-0.06%, dispersion tank is airtight, connect compressed air, control flow 60-100ml/min, slurries are inputted in the fluidisation reaction bed, and through 600-650 ℃ of fluid bed fluidized state dehydration and oxidation 35-38min, obtaining granularity is 700-800nm grained catalyst CoO-PdO-ZrO
2-La
2O
3/ SiO
2
2, the method for the dichloroethanes synthesis of ethylenediamine under the effect of above-mentioned catalyst, step is as follows:
(1) accurately taking by weighing above-mentioned grained catalyst in 1.15%～5.68% ratio of reacting processing industry dichloroethanes material weight also circulates in the reactor in the adding, closed reactor, the pure water of adding accurate-metering with pressure is used inert gas replacement, after being heated to 185 ℃ under stirring, pass into (H
2+ N
2) gaseous mixture, control system pressure is no more than 0.6Mpa, reacts after 180 minutes, leads to cooling water temperature to room temperature,
(2) liquefied ammonia of adding amount of calculation with pressure so that reactor in ammonia concn 35%, be heated to 95 ℃,
(3) add slow industrial dichloroethanes with high-pressure metering pump, so that liquefied ammonia/dichloroethanes molecular proportion 2.3,98-108 ℃ of control reaction temperature, treat that industrial dichloroethanes adds complete, 108 ± 2 ℃ of control temperature of reaction system were kept approximately 20 minutes, course of reaction is namely finished in cooling.
Above-mentioned catalysis dichloroethanes synthesis of ethylenediamine new technology has realized under the catalyst action, reduce ammonia and dichloroethanes mol ratio and using low concentration ammoniacal liquor can obtain the key technology of the ethylenediamine of high yield, wherein mol ratio drops to 1.2～2.6: 1, temperature is 98～110 ℃, the aminating reaction time is 60% of uncatalysed processes, optionally control distribution of reaction products by adding a certain proportion of effective catalyst, reaction time is shortened, make the principal product ethylenediamine have reaction selectivity, the polycaprolactam polyamine high-boiling components of generation is less than 0.5%.Catalysis dichloroethanes synthesis of ethylenediamine supports amine reaction overall selectivity 97%～98%, dichloroethanes conversion ratio 99.5%～100% selectively greater than 70% more.
Several catalyst are used for reaction result such as the following table one that dichloroethanes catalyzes and synthesizes ethylenediamine:
Table one: the transition-metal catalyst dichloroethanes catalyzes and synthesizes the reaction result of ethylenediamine
Annotate: the mensuration of dichloroethanes conversion ratio adopts the content of dichloroethanes in the system of chemical titration detection reaction front and back.Chromatography is adopted in the detection of ethylenediamine and other multi-enamine.
Claims (8)
1. catalyst that is used for the dichloroethane law synthesis of ethylenediamine, the active component that it is characterized in that this catalyst is three to four kinds of metals, it is 35-45% that metal active constituent accounts for total catalyst weight percentage, all the other components are oxygen element and the framework silica that match with metal active constituent, the basis of described metal active constituent is Co and a kind of lanthanide series metal, Co accounts for the 75%-78% of metal active constituent gross weight, lanthanide series metal accounts for the 8%-10% of metal active constituent gross weight, supplementary element in the described metal active constituent is Mo, W, Ni, Sn, Ru, Pd, Pb, Bi, Fe, Mn, Ti, among the Zr one or both, when described supplementary element is metal Ru or Pd, its weight accounts for respectively the 0.28-3.0% of total catalyst weight, described supplementary element is Mo, W, Ni, Sn, Ru, Pd, Pb, Bi, Fe, Mn, during among Ti and the Zr two kinds, the content sum of two kinds of metal ingredients accounts for the 12-17% of catalyst activity component total amount, and the atomic ratio of two kinds of metals is 1:1.
2. the catalyst for the dichloroethane law synthesis of ethylenediamine according to claim 1, it is characterized in that: described supplementary element is Mo, Ru, Pd, Bi, Fe or Zr preferably.
3. the catalyst for the dichloroethane law synthesis of ethylenediamine according to claim 1, it is characterized in that: the granularity of described catalyst is 700-800nm, total specific surface 380～430 m
2/ g, pore volume 0.68～0.73 mL/g.
4. method for preparing the catalyst for the dichloroethane law synthesis of ethylenediamine as claimed in claim 1 is characterized in that may further comprise the steps:
⑴ take by weighing respectively the soluble-salt of metal in the activity component metal oxide, is made into respectively the slaine working solution of molar content 0.008-0.015M, places recorder jar separately, and configuration alkali precipitation agent solution places recorder jar;
⑵ add pure water in the retort, be heated to 97 ± 2 ℃ under stirring, multiply and stream add 4 kinds of working metal liquid, stir 280-300 rev/min of revolution, the fully isoelectric point of precipitation according to slaine in the raw material slowly adds the alkali precipitation agent, the flow of control alkali precipitation agent, adopt echelon PH swinging method to realize the precipitation of metal, PH swings 5-8 time repeatedly, sour side PH=3.8, alkali side=10.3, reaction end PH=3.8-4.0, whole time 170-180 minute, simultaneously by adding water management colloidal dispersion solid content 0.5%-2.0% g/L, after reaction finishes, whole system 120-150 ℃ of crystallization 36 hours, is then regulated PH=7.8-8.0, crystallization 36 hours again under 120-150 ℃, filter, get filter cake, with filter cake with the pure water washing for several times, until wash water electrical conductivity ≯ 10 μ s/cm;
⑶ mix with carrier silica the rear qualified cake that obtains of step ⑵ washing by adding water, be adjusted to slurries, and the control solid content 880-900 rev/min, pulp 55-60 minute, is regulated PH=4.8-6.0 at 1.0-5.0%;
⑷ add the binding agent methylated cellulose aqueous solution in above-mentioned mixed serum, guarantee that the weight final concentration of methylcellulose in system is 0.05-0.06%, dispersion tank is airtight, connect compressed air, control flow 60-100ml/min, slurries are inputted in the fluidisation reaction bed, and through 600-650 ℃ of fluid bed fluidized state dehydration and oxidation, obtaining granularity is the 700-800nm grained catalyst.
5. the preparation method of the catalyst for the dichloroethane law synthesis of ethylenediamine according to claim 4 is characterized in that described carrier is silica and adds with the form of Ludox or silester.
6. the preparation method of the catalyst for the dichloroethane law synthesis of ethylenediamine according to claim 4, the soluble-salt that it is characterized in that described metal is solubility nitrate or the soluble-salt hydrochlorate of metal or the solubility acetate of metal of metal, and wherein Mo, W are oxysalt.
7. the preparation method of the catalyst for the dichloroethane law synthesis of ethylenediamine according to claim 4 is characterized in that described alkali precipitation agent is NaOH, sodium carbonate, ammonium hydroxide or organic amine, and wherein organic amine is triethylamine or n-butylamine.
8. the method for an application such as the arbitrary described catalyst dichloroethanes synthesis of ethylenediamine of claim 1-3 is characterized in that may further comprise the steps:
⑴ 1.15%～5.68% ratio that add the dichloroethanes raw material weight in reaction accurately take by weighing catalyst and add in circulate in the reactor, closed reactor, add water, use inert gas replacement, after being heated to 180-190 ℃ under stirring, pass into the H2+N2 gaseous mixture, control system pressure is no more than 0.6Mpa, react after 160-200 minute, be cooled to room temperature;
⑵ add liquefied ammonia, makes ammonia concn 35% in the reactor, is heated to 90-100 ℃;
⑶ add dichloroethanes, so that liquefied ammonia/dichloroethanes molecular proportion 1.2～2.6: 1,98-108 ℃ of control reaction temperature treats that dichloroethanes adds complete, and 108 ± 2 ℃ of control temperature of reaction system were kept 15-25 minute, and course of reaction is namely finished in cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110040741 CN102151571B (en) | 2011-02-18 | 2011-02-18 | Catalyst for synthesizing ethylene diamine via dichloroethane method, preparation method thereof and method for synthesizing ethylene diamine by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110040741 CN102151571B (en) | 2011-02-18 | 2011-02-18 | Catalyst for synthesizing ethylene diamine via dichloroethane method, preparation method thereof and method for synthesizing ethylene diamine by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102151571A CN102151571A (en) | 2011-08-17 |
| CN102151571B true CN102151571B (en) | 2013-02-13 |
Family
ID=44433438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110040741 Expired - Fee Related CN102151571B (en) | 2011-02-18 | 2011-02-18 | Catalyst for synthesizing ethylene diamine via dichloroethane method, preparation method thereof and method for synthesizing ethylene diamine by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102151571B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108311159A (en) * | 2018-04-15 | 2018-07-24 | 陕西理工大学 | A kind of catalyst and its synthetic method for synthesizing triethylene tetramine |
| CN111470973B (en) * | 2020-05-26 | 2022-07-12 | 河北工业大学 | Method for directly synthesizing binary organic amine by catalytic ammoniation of biomass glycerol |
-
2011
- 2011-02-18 CN CN 201110040741 patent/CN102151571B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102151571A (en) | 2011-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101745403B (en) | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas | |
| CN110961110B (en) | Catalyst and application thereof in 2,3,6-trichloropyridine hydrodechlorination | |
| CN102716749B (en) | Auxiliary agent-modified catalyst for CO-CO2 co-hydrogenation synthesis of methanol | |
| CN109569695B (en) | Preparation method and use method of core-shell structure catalyst for carbon dioxide hydrogenation | |
| CN110947382B (en) | Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof | |
| CN101007281A (en) | Novel preparation method of amorphous alloy catalyst | |
| CN103539635B (en) | Method for preparing isopropyl alcohol by acetone hydrogenation | |
| CN103372453A (en) | Catalyst for synthesis of methyl glycolate and preparation method thereof | |
| CN104588023A (en) | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN108499566A (en) | A kind of preparation method and application of CuNi bases catalyst | |
| CN103657658A (en) | Carboxylic ester hydrogenation catalyst and method for preparing cyclohexanol and ethanol | |
| CN101972657A (en) | Catalyst for hydrogenating silicon tetrachloride for preparing trichlorosilane and preparation method thereof | |
| CN110560054B (en) | 2, 4-dinitroaniline hydrogenation catalyst and preparation method and application thereof | |
| CN101920199B (en) | Fischer-Tropsch synthesis cobalt-based catalyst using modified silica gel as carrier and preparation method thereof | |
| CN102151571B (en) | Catalyst for synthesizing ethylene diamine via dichloroethane method, preparation method thereof and method for synthesizing ethylene diamine by using same | |
| CN115672327A (en) | High specific surface area superfine nano catalyst and preparation method and application thereof | |
| CN102485711B (en) | A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine | |
| CN101829567A (en) | Preparation method and application of load type nano-gold catalyst | |
| CN105772000A (en) | Graphene oxide promoted copper-based methanol synthesis catalyst and preparation method thereof | |
| CN103785391A (en) | High-activity Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN114054034B (en) | Multi-element copper-based non-noble metal hydrogenation catalyst, and preparation method and application thereof | |
| CN113101968A (en) | Catalyst and method for preparing glycine methyl ester and glycine by catalyzing and aminating methyl glycolate | |
| CN103566933B (en) | A kind of acetate preparation of ethanol by hydrogenating catalyst and preparation method thereof | |
| CN109759104B (en) | Preparation method of catalyst for low-temperature methanol synthesis | |
| CN101269332A (en) | Process for producing iron group fischer-tropsch synthesis catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210416 Address after: 213125 Xue Jia Zhen Lu Shu Ren Ge Cun, Xinbei District, Changzhou City, Jiangsu Province Patentee after: CHANGZHOU TIANLAN ELECTRONIC MATERIALS FACTORY Address before: 300384 Tianjin city Nankai District Zhuyuan Huayuan Industrial Zone Road No. 6 Building No. 2 room 4-203 Patentee before: TIANJIN KAIRUITE TECHNOLOGY Co.,Ltd. Patentee before: CHANGZHOU TIANLAN ELECTRONIC MATERIALS FACTORY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210604 Address after: 213022 room 812, building 7, fuhanyuan, Xinbei District, Changzhou City, Jiangsu Province Patentee after: Changzhou Jingxing Zerui Technology Co.,Ltd. Address before: 213125 Xue Jia Zhen Lu Shu Ren Ge Cun, Xinbei District, Changzhou City, Jiangsu Province Patentee before: CHANGZHOU TIANLAN ELECTRONIC MATERIALS FACTORY |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130213 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |