CN104923223A - Preparation method and application of selective hydrogenation catalyst - Google Patents
Preparation method and application of selective hydrogenation catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method and an application of a selective hydrogenation catalyst, and is used for mainly solving the problem that the dialkene hydrogenation selectivity is low in the prior art. The problem is better solved by adopting the technical schemes that the surface layer of a carrier is loaded with an organic chelate having a precious metal complexing ability by a spraying method to be modified, so as to obtained a modified carrier loaded with the precious metal component, then a modification agent and a cocatalyst are loaded by the spraying method, and finally dry roasting reduction is carried out. The preparation method can be used in industrial production of selective hydrogenation of dialkene into monoolefin.
Description
Technical field
The present invention relates to a kind of Preparation method and use for diolefin hydrogenate catalyst, the long chain hydrocarbon selec-tive hydrogenation be particularly useful for containing alkadienes is monoolefine.
Background technology
Long-chain (C
6~ C
20) monoolefine is important as precursors in washing agent preparation process.Most of washing agent is obtained by LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 ester in the market, and benzene sulfonamide acid esters then derives from alkylbenzene.In large-scale industrial production, be the alkene of correspondence by linear alkanes dehydrogenation by dehydrogenation reaction, then under the effect of acid catalyst, produce alkylbenzene with benzene generation alkylated reaction.In the certain embodiments of linear paraffin, wish that the product obtained is monoolefine most, but, owing to optionally limiting, inevitably produce a part of alkadienes.The generation of generation to next step alkylbenzene of alkadienes has adverse effect, therefore, needs to be removed by certain method, and di-olefins is monoolefine by the method for current industrial main employing selec-tive hydrogenation.
Along with clean gasoline demand increases day by day, alkylate oil because of its octane number high, sensitiveness is little, has become the ideal composition of reformulated gasoline.Thus alkylate oil is produced more aobvious important.Hydrogen fluoride alkylation is one of main technique of refinery's production high-quality clean gasoline.The general alkadienes containing 0.3-0.5% in raw material for alkylation.In alkylated reaction, alkadienes can generate the higher oil of relative molecular weight, causes alkylate oil Quality Down, and reaction acid consumption increases.The preferred approach addressed this problem adopts selective hydrogenation method removing alkadienes.
Generally speaking, the saturated reaction of alkadienes is very fast, can complete under lower temperature and high-speed condition.If conjugated diene can occur superimposed under common hydroprocessing condition (high temperature low-speed), superimposed product can induce reaction device fouling, and Pressure Drop is increased, and incrustation is accumulated on catalyst, makes catalyst inactivation gradually.Meanwhile, if containing more monoolefine in raw material, when catalyst choice is not good, the saturated meeting of monoolefine produces very large temperature rise in the reactor, and then makes more monoolefine saturated, causes the monoolefine in raw material to lose.Therefore, desirable catalyst must have the saturated high selectivity of alkadienes, and to monoolefine saturated have low selective.
At present, what the catalyst of industrial alkadienes or other unsaturated fraction selective hydrogenations was mainly applied is nickel sulfide catalyst, and reaction temperature is 180 DEG C.Due in course of reaction, sulphur can from catalyst loss to product in, therefore, sulphur must be supplemented to keep the optimum activity of catalyst, and owing to being mixed into sulphur in product, in order to obtain the product cleaned, also sulphur must be removed, this just further increases operation and cost.Patent US4992157 describes a kind of nickel sulfide catalyst, by by nickel sulfide load on alumina support or other clay carrier, be prepared into loaded catalyst, then hydrocarbon is made to contact at catalyst surface with hydrogen, make the impurity selective hydrogenations such as the double bond in raw material, to improve quality of colour and the colour stability of raw material, the advantage of the program is the use of comparatively cheap metallic nickel, shortcoming is the introduction of sulphur, and raw material may be made to be polluted.
Patent CN200810133328.5 reports a kind of carbon monoxide-olefin polymeric of layering.This catalyst has the coating such as gama-alumina of a kernel such as Alpha-alumina and an inorganic oxide.On skin equably load platinum metal if palladium and co-catalyst are as copper, catalyst also containing a kind of dressing agent as potassium.For the selec-tive hydrogenation of alkadienes.Its shortcoming is that the preparation process of catalyst is comparatively complicated, and alkadienes is selective not high.
Summary of the invention
One of technical problem to be solved by this invention is that the preparation process of the diolefin hydrogenate catalyst existed in prior art is complicated, and the selective low problem of diene hydrogenation, provides a kind of new selective hydrocatalyst.Catalyst prepared by the present invention has that preparation process is simple, the selective high advantage of diene hydrogenation.Two of technical problem to be solved by this invention is to provide the method for a kind of catalyst corresponding with solving one of relevant art problem for selective hydrogenation.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of selective hydrocatalyst, comprises the following steps:
A. shaping carrier is prepared;
B. support modification: under 30 ~ 80 DEG C of heated-air dryings, by the solution spraying containing organic sequestering agent on carrier, 50 ~ 90 DEG C of dryings, obtain modified support; Described containing in the solution of organic sequestering agent, organic sequestering agent is selected from three n-octylamine, trioctylphosphine oxide (TOPO), tributyl phosphate, N, N-dimethyl amine, N, N-diethyl-1,4 pentanediamines, decamethylene diamine, acetic acid, N, at least one in N-dimethyl dodecylamine, solvent is selected from least one in water, ethanol, acetone;
C. load active component: the aqueous solution of preparation precious metal chemical complex, noble metal is selected from least one in ruthenium, rhodium, palladium, osmium, iridium, platinum, gold; The modified support obtained by step b joins in the aqueous solution of precious metal chemical complex and floods, and is filtered dry, dry;
D. load dressing agent and co-catalyst: the presoma of dressing agent and co-catalyst is made into the aqueous solution, is sprayed on the carrier of the load active component obtained by step c, obtains catalyst precursor;
E. catalyst precursor steps d obtained is dry, roasting, obtained catalyst.
In technique scheme, the shaping carrier in step a is preferably selected from least one in cordierite, aluminium oxide, silica, zirconia, titanium oxide, magnesia, zeolite, molecular sieve, carborundum; The mol ratio of organic sequestering agent and noble metal is preferably (1 ~ 10): 1, is more preferably (3 ~ 4): 1; Precious metal chemical complex in step c is preferably selected from chloroplatinic acid, palladium bichloride, at least one in palladium nitrate, rhodium nitrate, platinous chloride, platinum tetrachloride, ammonium chloroplatinate, platinum nitrate, dichloro four ammino platinum, dinitroso diammonia platinum; Noble metal in step c is preferably palladium, and consumption is preferably 0.01% ~ 5.0% of catalyst weight; Dressing agent in steps d is preferably selected from least one in tin, germanium, lead, and consumption is preferably 0.1% ~ 5.0% of catalyst weight; Co-catalyst in steps d is preferably selected from least one in lithium, sodium, magnesium, potassium, calcium, strontium, barium, and consumption is preferably 0.1% ~ 2.0% of catalyst weight.
Baking temperature in the present invention in step c is preferably 60 ~ 120 DEG C; Drying in step e and roasting condition are preferably: 100 ~ 150 DEG C of dryings 1 ~ 24 hour, 200 ~ 700 DEG C of roastings 1 ~ 24 hour.In addition, catalyst in reducing atmosphere (as hydrogen), need reduce 1 ~ 4 hour at 300 ~ 800 DEG C before use.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of method of selective hydrogenation, with containing the C of alkadienes
6hydrocarbon ~ C
20hydrocarbon and hydrogen are raw material, are 20 ~ 150 DEG C in reaction temperature, and reaction pressure is 1 ~ 10MPa, and liquid air speed is 0.1 ~ 10 hour
-1, the mol ratio of hydrogen and alkadienes is under the condition of 1 ~ 10, and raw material and catalyst exposure, react, and makes the diolefin hydrogenate in raw material be monoolefine; The preparation method of described catalyst comprises the following steps:
A. shaping carrier is prepared;
B. support modification: under 30 ~ 80 DEG C of heated-air dryings, by the solution spraying containing organic sequestering agent on carrier, 50 ~ 90 DEG C of dryings, obtain modified support; Described containing in the solution of organic sequestering agent, organic sequestering agent is selected from three n-octylamine, trioctylphosphine oxide (TOPO), tributyl phosphate, N, N-dimethyl amine, N, N-diethyl-1,4 pentanediamines, decamethylene diamine, acetic acid, N, at least one in N-dimethyl dodecylamine, solvent is selected from least one in water, ethanol, acetone;
C. load active component: the aqueous solution of preparation precious metal chemical complex, noble metal is selected from least one in ruthenium, rhodium, palladium, osmium, iridium, platinum, gold; The modified support obtained by step b joins in the aqueous solution of precious metal chemical complex and floods, and is filtered dry, dry;
D. load dressing agent and co-catalyst: the presoma of dressing agent and co-catalyst is made into the aqueous solution, is sprayed on the carrier of the load active component obtained by step c, obtains catalyst precursor;
E. catalyst precursor steps d obtained is dry, roasting, obtained catalyst.
In technique scheme, reaction temperature is preferably 55 ~ 150 DEG C, and reaction pressure is preferably 2 ~ 4MPa, and liquid air speed is preferably 3 ~ 6 hours
-1, the mol ratio of hydrogen and alkadienes is preferably 1 ~ 5.
The shaping carrier that the present invention adopts the forming methods known arbitrarily such as extrusion, spin, pressure ball to prepare.Carrier can make different shapes as required, as cylindric, spherical, sheet, tubular, cellular or Raschig ring etc., but spherical be reasonable selection, its diameter is preferably 1 ~ 5 millimeter, so that commercial Application.
In concept of the present invention, di-olefins rate and and monoolefine is selective is obtained by following account form:
Catalyst of the present invention is based on noble metal Coordinative Chemistry theory, by the chelation of part, is anchored to by precious metal atom and is positioned on the organic chelate of carrier surface, thus effectively disperse noble metal.The units activity component utilization rate of gained catalyst is high, can play the catalytic action of active metal expeditiously, and be conducive to the carrying out of diolefin hydrogenate reaction, making prepared catalyst have excellent diolefin hydrogenate is the selective of monoolefine.Chelation simultaneously due to organic ligand is very strong, the noble metal in precious metal impregnation liquid 100% can be adsorbed onto carrier surface, eliminates the steps such as the enrichment recycling of the noble metal in the remaining liquid of dipping, simplifies the preparation process of noble metal catalyst.
Adopt the catalyst that the inventive method is obtained, at the C containing alkadienes
6hydrocarbon ~ C
20in the selective hydrogenation of hydrocarbon, be 3MPa in reaction pressure, liquid air speed is 6 hours
-1, reaction temperature is 60 DEG C, and the mol ratio of hydrogen and alkadienes is under the condition of 1.5, and di-olefins rate reaches 76.8%, and monoolefine is selective reaches 91.3%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated, but these embodiments can not limit scope of the present invention.
Detailed description of the invention
[embodiment 1]
Three n-octylamine 0.0544 gram is dissolved in wiring solution-forming in 50 milliliters of ethanol, under 30 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.4 grams of alumina balls (diameter 2 ~ 4 millimeters) carrier, 50 DEG C of dryings.By load, the carrier of organic ligand drops in the chloroplatinic acid aqueous solution of 0.03 gram, 50 milliliters of containing metal platinum, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 60 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.03 gram with containing the lithium chloride of lithium 0.48 gram, even application in load on the carrier of noble metal, 100 DEG C of dryings 24 hours, 200 DEG C of roastings 24 hours, 300 DEG C are reduced 4 hours, obtain catalyst A 1 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 2]
Trioctylphosphine oxide (TOPO) 0.0178 gram is dissolved in wiring solution-forming in 50 milliliters of ethanol, under 30 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.5 grams of cylindrical titanium oxide (diameter 2 millimeters, long 5 ~ 10 millimeters) carrier, 50 DEG C of dryings.By load, the carrier of organic ligand drops in the platinum nitrate aqueous solution of 0.003 gram, 50 milliliters of containing metal platinum, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 100 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.24 gram with containing the potassium nitrate of 0.30 gram, potassium, even application in load on the carrier of noble metal, 110 DEG C of dryings 12 hours, 400 DEG C of roastings 12 hours, 350 DEG C are reduced 4 hours, obtain catalyst A 2 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 3]
Tributyl phosphate 0.0410 gram is dissolved in wiring solution-forming in 50 milliliters of ethanol, under 30 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.6 grams of cylindrical magnesia (diameter 2 millimeters, long 5 ~ 10 millimeters) carrier, 60 DEG C of vacuum drying.By load, the carrier of organic ligand drops in the palladium chloride aqueous solution of 50 milliliters of containing metal palladiums 0.015 gram, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 80 DEG C of vacuum drying.The calcium chloride of the plumbi nitras of leaded 0.18 gram and calcic 0.24 gram is made into 20 ml water solution, even application in load on the carrier of noble metal, 120 DEG C of dryings 12 hours, 400 DEG C of roastings 12 hours, 300 DEG C are reduced 4 hours, obtain catalyst A 3 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 4]
Acetic acid 4.6154 grams is dissolved in wiring solution-forming in 50 ml waters, under 50 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 27.3 grams of spherical carbide silicon (diameter 2 ~ 4 millimeters) carrier, 60 DEG C of vacuum drying.By load, the carrier of organic ligand drops in the chloroplatinic acid aqueous solution of 1.50 grams, 50 milliliters of containing metal platinum, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 60 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.60 gram with containing the strontium chloride of 0.60 gram, strontium, even application in load on the carrier of noble metal, 100 DEG C of dryings 24 hours, 250 DEG C of roastings 18 hours, 400 DEG C are reduced 3 hours, obtain catalyst A 4 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 5]
N, N-dimethyl amine 0.0225 gram is dissolved in wiring solution-forming in 50 milliliters of ethanol, under 50 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.5 grams of cylindrical zirconium oxide (diameter 2 millimeters, long 5 ~ 10 millimeters) carrier, 70 DEG C of dryings.By load, the carrier of organic ligand drops in the ammonium chloroplatinate aqueous solution of 0.03 gram, 50 milliliters of containing metal platinum, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 80 DEG C of vacuum drying.The barium chloride of the germanium tetrachloride of germanic 0.36 gram and baric 0.12 gram is made into 20 ml water solution, even application in load on the carrier of noble metal, 150 DEG C of dryings 4 hours, 500 DEG C of roastings 6 hours, 300 DEG C are reduced 4 hours, obtain catalyst A 5 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 6]
N, N-diethyl-Isosorbide-5-Nitrae pentanediamine 0.0877 gram is dissolved in wiring solution-forming in 50 milliliters of acetone, under 50 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.3 grams of cylindrical wire geolytes and aluminium oxide mixing (diameter 2 millimeters, long 5 ~ 10 millimeters) carrier, 70 DEG C of dryings.By load, the carrier of organic ligand drops in the palladium nitrate aqueous solution of 50 milliliters of containing metal palladiums 0.036 gram, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 60 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.48 gram with containing the lithium nitrate of lithium 0.18 gram, even application in load on the carrier of noble metal, 100 DEG C of dryings 24 hours, 300 DEG C of roastings 12 hours, 400 DEG C of reductase 12s hour in hydrogen atmosphere, obtain catalyst A 6.Catalyst property is in table 1.
[embodiment 7]
Decamethylene diamine 0.1233 gram is dissolved in wiring solution-forming in 50 milliliters of ethanol, and under 60 DEG C of heated-air dryings, this dissolution homogeneity being sprayed at 29.8 grams of kernels is on outer bead (diameter 2 ~ 4 millimeters) carrier for aluminium oxide of cordierite, 70 DEG C of dryings.By load, the carrier of organic ligand drops in the palladium nitrate aqueous solution of 50 milliliters of containing metal palladiums 0.03 gram, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 80 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.12 gram with containing the lithium chloride of lithium 0.06 gram, even application in load on the carrier of noble metal, 120 DEG C of dryings 12 hours, 550 DEG C of roastings 4 hours, 300 DEG C are reduced 3 hours, obtain catalyst A 7 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 8]
By N, N-dimethyl dodecylamine 0.1313 gram is dissolved in wiring solution-forming in 50 milliliters of ethanol, under 60 DEG C of heated-air dryings, this dissolution homogeneity is sprayed at 29.4 grams of cylindrical Y molecular sieves and silica mixing (diameter 2 millimeters, long 5 ~ 10 millimeters) on carrier, 80 DEG C of vacuum drying.By load, the carrier of organic ligand drops in the dinitroso diammonia platinum aqueous solution of 0.03 gram, 50 milliliters of containing metal platinum, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 100 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.54 gram with containing the lithium chloride of lithium 0.03 gram, even application in load on the carrier of noble metal, 120 DEG C of dryings 12 hours, 450 DEG C of roastings 12 hours, 500 DEG C are reduced 1 hour, obtain catalyst A 8 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 9]
Three n-octylamine 0.2176 gram is dissolved in wiring solution-forming in 50 milliliters of acetone, under 60 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.6 grams of cloverleaf pattern aluminium oxide (diameter 2 millimeters, long 5 ~ 10 millimeters) carrier, 80 DEG C of vacuum drying.By load, the carrier of organic ligand drops in the dichloro four ammino platinum aqueous solution of 0.03 gram, 50 milliliters of containing metal platinum, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 60 DEG C of vacuum drying.20 ml water solution are made into by the germanium tetrachloride of germanic 0.24 gram with containing the sodium chloride of 0.12 gram, sodium, even application in load on the carrier of noble metal, 100 DEG C of dryings 24 hours, 600 DEG C of roastings 24 hours, 600 DEG C are reduced 1 hour, obtain catalyst A 9 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 10]
Three n-octylamine 4.8047 grams is dissolved in wiring solution-forming in 50 milliliters of ethanol, under 60 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.0 grams of preparing spherical SiO 2s (diameter 2 ~ 4 millimeters) carrier, 80 DEG C of dryings.By load, the carrier of organic ligand drops in the palladium chloride aqueous solution of 50 milliliters of containing metal palladiums 0.18 gram, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 120 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.30 gram with containing the magnesium chloride of 0.48 gram, magnesium, even application in load on the carrier of noble metal, 120 DEG C of dryings 24 hours, 500 DEG C of roastings 24 hours, 300 DEG C of reductase 12s hour in hydrogen atmosphere, obtain catalyst A 10.Catalyst property is in table 1.
[embodiment 11]
N, N-dimethyl dodecylamine 1.2079 grams is dissolved in wiring solution-forming in 50 milliliters of ethanol, under 70 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.6 grams of ball-aluminium oxides (diameter 2 ~ 4 millimeters) carrier, 80 DEG C of dryings.By load, the carrier of organic ligand drops in the platinum nitrate aqueous solution of 50 milliliters of containing metal palladiums 0.15 gram, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 60 DEG C of vacuum drying.20 ml water solution are made into by the germanium tetrachloride of germanic 0.06 gram with containing the sodium nitrate of 0.18 gram, sodium, even application in load on the carrier of noble metal, 150 DEG C of dryings 8 hours, 600 DEG C of roastings 2 hours, 700 DEG C are reduced 1 hour, obtain catalyst A 11 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 12]
N, N-diethyl-Isosorbide-5-Nitrae pentanediamine 1.3831 grams is dissolved in wiring solution-forming in 50 milliliters of acetone, under 70 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 29.1 grams of cylindrical shaped alumina (diameter 2 millimeters, long 5 ~ 10 millimeters) carrier, 80 DEG C of dryings.By load, the carrier of organic ligand drops in the rhodium nitrate aqueous solution of 50 milliliters of containing metal rhodiums 0.15 gram, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 60 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.24 gram with containing the lithium chloride of lithium 0.54 gram, even application in load on the carrier of noble metal, 100 DEG C of dryings 24 hours, 500 DEG C of roastings 6 hours, 800 DEG C are reduced 1 hour, obtain catalyst A 12 in hydrogen atmosphere.Catalyst property is in table 1.
[embodiment 13]
Decamethylene diamine 2.3343 grams is dissolved in wiring solution-forming in 50 milliliters of ethanol, under 80 DEG C of heated-air dryings, this dissolution homogeneity is sprayed on 27.7 grams of cylindrical shaped alumina (diameter 2 millimeters, long 5 ~ 10 millimeters) carrier, 90 DEG C of dryings.By load, the carrier of organic ligand drops in the rhodium nitrate aqueous solution of 50 milliliters of containing metal rhodiums 0.60 gram, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 120 DEG C of vacuum drying.20 ml water solution are made into by the plumbi nitras of leaded 1.50 grams with containing the magnesium nitrate of 0.18 gram, magnesium, even application in load on the carrier of noble metal, 150 DEG C of dryings 1 hour, 700 DEG C of roastings 1 hour, 300 DEG C of reductase 12s hour in hydrogen atmosphere, obtain catalyst A 13.Catalyst property is in table 1.
[comparative example 1]
Do not use the solution treatment carrier containing organic sequestering agent, be directly that outer bead (diameter 2 ~ 4 millimeters) carrier for aluminium oxide of cordierite drops in the palladium nitrate aqueous solution of 50 milliliters of containing metal palladiums 0.03 gram by 29.8 grams of kernels, mechanical agitation 5 minutes (300 revs/min), centrifuge dripping, 80 DEG C of vacuum drying.20 ml water solution are made into by the butter of tin of stanniferous 0.12 gram with containing the lithium chloride of lithium 0.06 gram, even application in load on the carrier of noble metal, 120 DEG C of dryings 12 hours, 550 DEG C of roastings 4 hours, 300 DEG C are reduced 3 hours, obtain catalyst B 1 in hydrogen atmosphere.
[comparative example 2]
By nickel nitrate aqueous solution equivalent impregnation on 30 grams of cylindrical shaped alumina carriers, 120 DEG C of dryings 12 hours, then 550 DEG C of roastings 2 hours, use 10% hydrogen sulfide/90% nitrogen, 350 DEG C of sulfurations 12 hours, obtain the nickel sulfide catalyst B 2 of nickeliferous (in metallic nickel) 10%.
[embodiment 14]
The present embodiment illustrates that embodiment 1 ~ 13 gained catalyst is at C
6~ C
20application in the selective hydrogenation of alkadienes.
Getting the embodiment of the present invention 1 ~ 13 gained catalyst each 30ml loading internal diameter is carry out reaction examination in the stainless steel reaction pipe of 25 millimeters.Reaction raw materials composition is in table 2.Reaction condition is: reaction pressure is 3MPa, liquid air speed 6 hours
-1, the mol ratio of hydrogen and alkadienes is 1.5, and reaction temperature is 60 DEG C.Reaction result is in table 3.As can be seen from the table, the catalyst that prepared by this method there is higher di-olefins rate compared with reference catalyst and monoolefine selective.
[comparative example 3]
Getting comparative example 1,2 gained catalyst each 30ml loading internal diameter is carry out reaction examination in the stainless steel reaction pipe of 25 millimeters.Raw material similarly to Example 14 and reaction condition (wherein the reaction temperature of catalyst B 2 is 190 DEG C) is adopted to carry out reaction examination.Reaction result is in table 3.
Table 1
* consumption is all with catalyst weight
Table 2
Table 3
[embodiment 15]
The present embodiment illustrates that embodiment 7 gained catalyst A 7 is at C
6~ C
20the result of the test of process conditions is changed in the selective hydrogenation of alkadienes.
Getting the embodiment of the present invention 7 gained catalyst A 730ml loading internal diameter is carry out reaction examination in the stainless steel reaction pipe of 25 millimeters, changes process conditions and tests.Reaction raw materials composition is in table 1, and reaction result is in table 4.
Table 4
Claims (10)
1. a preparation method for selective hydrocatalyst, comprises the following steps:
A. shaping carrier is prepared;
B. support modification: under 30 ~ 80 DEG C of heated-air dryings, by the solution spraying containing organic sequestering agent on carrier, 50 ~ 90 DEG C of dryings, obtain modified support; Described containing in the solution of organic sequestering agent, organic sequestering agent is selected from three n-octylamine, trioctylphosphine oxide (TOPO), tributyl phosphate, N, N-dimethyl amine, N, N-diethyl-1,4 pentanediamines, decamethylene diamine, acetic acid, N, at least one in N-dimethyl dodecylamine, solvent is selected from least one in water, ethanol, acetone;
C. load active component: the aqueous solution of preparation precious metal chemical complex, noble metal is selected from least one in ruthenium, rhodium, palladium, osmium, iridium, platinum, gold; The modified support obtained by step b joins in the aqueous solution of precious metal chemical complex and floods, and is filtered dry, dry;
D. load dressing agent and co-catalyst: the presoma of dressing agent and co-catalyst is made into the aqueous solution, is sprayed on by step
On the carrier of the load active component that c obtains, obtain catalyst precursor;
E. catalyst precursor steps d obtained is dry, roasting, obtained catalyst.
2. the preparation method of selective hydrocatalyst according to claim 1, the shaping carrier that it is characterized in that in step a is selected from least one in cordierite, aluminium oxide, silica, zirconia, titanium oxide, magnesia, zeolite, molecular sieve, carborundum.
3. the preparation method of selective hydrocatalyst according to claim 1, is characterized in that the mol ratio of organic sequestering agent and noble metal is for (1 ~ 10): 1.
4. the preparation method of selective hydrocatalyst according to claim 3, is characterized in that the mol ratio of organic sequestering agent and noble metal is for (3 ~ 4): 1.
5. the preparation method of selective hydrocatalyst according to claim 1, it is characterized in that the precious metal chemical complex in step c is selected from chloroplatinic acid, palladium bichloride, at least one in palladium nitrate, rhodium nitrate, platinous chloride, platinum tetrachloride, ammonium chloroplatinate, platinum nitrate, dichloro four ammino platinum, dinitroso diammonia platinum.
6. the preparation method of selective hydrocatalyst according to claim 1, it is characterized in that the noble metal in step c is palladium, consumption is 0.01% ~ 5.0% of catalyst weight.
7. the preparation method of selective hydrocatalyst according to claim 1, the dressing agent that it is characterized in that in steps d is selected from least one in tin, germanium, lead, and consumption is 0.1% ~ 5.0% of catalyst weight.
8. the preparation method of selective hydrocatalyst according to claim 1, the co-catalyst that it is characterized in that in steps d is selected from least one in lithium, sodium, magnesium, potassium, calcium, strontium, barium, and consumption is 0.1% ~ 2.0% of catalyst weight.
9. a method for selective hydrogenation, with the C containing alkadienes
6hydrocarbon ~ C
20hydrocarbon and hydrogen are raw material, are 20 ~ 150 DEG C in reaction temperature, and reaction pressure is 1 ~ 10MPa, and liquid air speed is 0.1 ~ 10 hour
-1, the mol ratio of hydrogen and alkadienes is under the condition of 1 ~ 10, and raw material and catalyst exposure, react, and makes the diolefin hydrogenate in raw material be monoolefine; Described catalyst adopts method according to claim 1 to prepare.
10. the method for selective hydrogenation according to claim 9, it is characterized in that reaction temperature is 55 ~ 150 DEG C, reaction pressure is 2 ~ 4MPa, and liquid air speed is 3 ~ 6 hours
-1, the mol ratio of hydrogen and alkadienes is 1 ~ 5.
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|---|---|---|---|---|
| CN109562354A (en) * | 2016-08-02 | 2019-04-02 | 沙特基础工业全球技术有限公司 | The method for being used to prepare hydrocracking catalyst |
| CN111185237A (en) * | 2020-02-19 | 2020-05-22 | 浙江大学 | Selective hydrogenation catalyst, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5148607A (en) * | 1974-10-16 | 1976-04-26 | Noguchi Kenkyusho | |
| US20060241313A1 (en) * | 2005-04-26 | 2006-10-26 | Archer-Daniels-Midland Company | Copper compositions and their use as hydrogenation catalysts |
| CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
| CN102641740A (en) * | 2011-02-22 | 2012-08-22 | 中国石油天然气股份有限公司 | Diene selective hydrogenation catalyst and preparation method thereof |
| CN103170349A (en) * | 2011-12-23 | 2013-06-26 | 中国石油化工股份有限公司 | Copper catalyst for selective hydrogenation of mixed C4 and preparation method of copper catalyst |
-
2014
- 2014-03-17 CN CN201410097495.4A patent/CN104923223B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5148607A (en) * | 1974-10-16 | 1976-04-26 | Noguchi Kenkyusho | |
| US20060241313A1 (en) * | 2005-04-26 | 2006-10-26 | Archer-Daniels-Midland Company | Copper compositions and their use as hydrogenation catalysts |
| CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
| CN102641740A (en) * | 2011-02-22 | 2012-08-22 | 中国石油天然气股份有限公司 | Diene selective hydrogenation catalyst and preparation method thereof |
| CN103170349A (en) * | 2011-12-23 | 2013-06-26 | 中国石油化工股份有限公司 | Copper catalyst for selective hydrogenation of mixed C4 and preparation method of copper catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109562354A (en) * | 2016-08-02 | 2019-04-02 | 沙特基础工业全球技术有限公司 | The method for being used to prepare hydrocracking catalyst |
| CN111185237A (en) * | 2020-02-19 | 2020-05-22 | 浙江大学 | Selective hydrogenation catalyst, preparation method and application thereof |
| CN111185237B (en) * | 2020-02-19 | 2020-11-06 | 浙江大学 | Selective hydrogenation catalyst, preparation method and application thereof |
| WO2021164099A1 (en) * | 2020-02-19 | 2021-08-26 | 浙江大学 | Selective hydrogenation catalyst, preparation method therefor and use thereof |
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| CN104923223B (en) | 2017-06-20 |
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