CN109833869A - A kind of slurry bed hydrogenation catalyst and its preparation method and application - Google Patents
A kind of slurry bed hydrogenation catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of slurry bed system liquid phase hydrogenating catalyst and its applications.The catalyst is with one of precious metals pd, Pt, Rh or several combinations for main active component, and carrier is mainly nitrogenous silica support, and the average pore size of the catalyst carrier is greater than 10nm, and Kong Rong is not higher than 0.7cc/g.Hydrogenation catalyst disclosed by the invention is by introducing amino group to carrier, to greatly improve the dispersion degree of noble metal, and then improves the activity for adding hydrogen and the dosage for reducing noble metal；The surface nature of nitrogenous silica support further improves the desorption for adding hydrogen intermediate product, to improve the selectivity of anthraquinone hydrogenation, activity and stability by the modification of amino simultaneously.Catalyst of the present invention can be used for during slurry bed system anthraquinone catalytic hydrogenation production hydrogen peroxide, at 40-60 DEG C of reaction temperature, pressure 0.05-0.3MPa, liquid air speed 60-300h‑1Under the conditions of, hydrogenation catalyst shows very high hydrogenation activity and good stability.
Description
Technical field
The invention belongs to petrochemical industries, and in particular to a kind of slurry bed hydrogenation catalyst and preparation method thereof and answer
With.
Background technique
The final product decomposed in hydrogen peroxide use process is mainly water, will not generate secondary pollution, is a kind of environment
Friendly chemicals.As the chemical products of green, hydrogen peroxide can be used as oxidant, bleaching agent, disinfectant, polymerization initiator
Deng being widely used in the industries such as chemical industry synthesis, papermaking, weaving, environmental protection, food, electronics, space flight.Not with Green Chemical Engineering Process
Disconnected development and national environmental protection regulation it is increasingly strict, especially hydrogen peroxide as Green Oxidant and environmental-friendly bleaching agent and
Disinfectant using increasingly extensive.Such as in green chemical industry field: caprolactam, cyclohexanone, hydroquinone, propylene oxide etc.
Emerging clean manufacturing process is using hydrogen peroxide as oxidant；In environment protection field: hydrogen peroxide is replacing hypochlorite to become master
The bleaching agent and disinfectant of stream, especially in terms of disinfection and sterilization, hydrogen peroxide is expected to substitution chlorine, as urban water
Bleaching and disinfectant.Currently, the hydrogen peroxide total productive capacity in the whole world has reached 22,000,000 tons/year, and hydrogen peroxide generative capacity
Increased with the speed of annual 8%~11%.At the same time, the hydrogen peroxide development in China is same rapid, since 2004, I
The hydrogen peroxide production capacity of state has reached 2,500,000 tons/year, has been more than that the U.S. becomes the maximum Hydrogen Peroxide Production state in the whole world.Pair in China
Oxygen water capacity and output is with annual 15%~20% or so speed increase, and the hydrogen peroxide production capacity in China has reached about at present
Ten thousand tons/year of 1100-1200 (with 27.5% densimeter).The main drive that the nearly 2 years Hydrogen Peroxide Production abilities in China increase be with
Hydrogen peroxide is the technological development success that raw material produces caprolactam and propylene oxide, and is further formed production scale, is needed big
The hydrogen peroxide raw material of amount.
Although the production method of hydrogen peroxide has electrolysis method, anthraquinone, isopropanol method and hydrogen-oxygen direct synthesis technique, mesh
It is preceding it is anthraquinone be still the main method of Hydrogen Peroxide Production on our times, the production capacity of technique accounts for whole 95%.And China
Enterprise's proportion using method production hydrogen peroxide has been more than 98%.Anthraquinone generation hydrogen peroxide is existed in catalyst first
In the case where, anthraquinone and hydrogen in working solution (mixture of organic solvent and working material anthraquinone) carry out hydrogenation catalyst reaction
Generate anthrahydroquinone；Oxygen occurs for followed by oxidation process, mainly anthrahydroquinone and oxygen, air or the mixed gas containing oxygen
Change reaction, anthrahydroquinone transforms into anthraquinone, and at the same time generating hydrogen peroxide；Followed by extraction process, life is reacted from working solution
At hydrogen peroxide extracted using water, so that hydrogen peroxide and working solution be made to be separated.It is finally last handling process, mainly
Working solution after removal hydrogen peroxide returns to above-mentioned hydrogenation catalyst reaction step after processing, so that formation one complete
Cyclic process.This cyclic process realizes hydrogen peroxide from two kinds of objects of hydrogen and air mainly by means of working solution carrier
The synthesis of matter, thus hydrogen dioxide solution production by anthraquinone process is an efficient process.
In anthraquinone hydrogenation technique, wherein mostly important step is the hydrogenation process of anthraquinone, the operation list hydrogenated at present
Member is mainly trickle bed and slurry bed system.The research of Santacesaria (Chem.Eng.Sci.1999,54,2799-2809) et al.
Point out that anthraquinone hydrogenation reaction is the reaction of mass transfer diffusion control, rate-determining steps be gas-liquid, liquid it is solid between mass transfer rate.Drip
Bed is that solid catalyst particle is fixed on inside reactor, and the catalyst granules of inside reactor filling is bigger (1-10mm),
Working fluid and hydrogen pass through beaded catalyst bed simultaneously.Although the operation of trickle bed is more convenient, since particle is urged
Agent accumulates the duct to be formed not and is very regular, causes the uneven distribution of liquids and gases, inevitably results in fluid
Channel and short circuit；And then soak catalyst surface will not by liquid all, cause the utilization rate of catalyst to reduce；And it causes
The contact surface of hydrogen, working solution and catalyst reduces, and the transmittance process of component is slow；In addition, in trickle bed fluid it is uneven
Mobility also will cause the inhomogeneity of hydrogenation process, in turn results in the anthraquinone hydrogenation overreact of part, forms not
Necessary by-product or precipitating.Although the flow velocity for increasing gas and liquid can improve above-mentioned situation, can make in this way
It is relatively high by the pressure drop of trickle bed at fluid, the loss of very high energy consumption and catalyst is caused, therefore in actual operation
Need to limit the flow velocity of gas and liquid.The radial direction mixing of this outer fluid on a catalyst is poor, and diabatic process is slow, because
And it will cause the hot localised points of trickle bed, and then will cause the temperature runaway of entire bed.All above-mentioned phenomenons cause trickle bed
Operating cost is high, and production capacity is low.
Slurry bed system is that solid catalyst is suspended in liquid medium, and then passing to gas is scattered in gas in liquid；Its
The particle scale of middle solid catalyst is usually quite small (5-200 μm).Compared to trickle bed reactor, slurry reactor utensil
It has the advantage that
Since the catalyst granules of use is smaller, there is relatively high efficiency factor, and in inside reactor, gas-liquid
Gu the phase contact area of three-phase is bigger (can be up to 3280-16400m2/m3), therefore it is than the catalyst granules of trickle bed
Reaction, mass transfer are much faster.The utilization rate of catalyst is improved, therefore, the slurry bed system production intensity of unit volume equipment wants high
In trickle bed；
Since catalyst mixes strongly in bed in slurry bed system, temperature and concentration distribution of the particle in full bed are uniform, bed
The heat transfer coefficient of layer core inner wall heat exchange area is higher, and the ratio of heat capacities of full bed is larger, and stability is high；
Slurry bed system endoparticle group has the property of tired quasi-fluid, can largely remove and introduce from device, and can be in 2 slurry
It is largely recycled between bed；
The way of contact of gas, liquid in slurry bed system and the heat transfer between solid particle, mass transfer compared with other reactors is
It is highest；
Since the variation of porosity in fluid fixed system can cause being widely varied for particle drag coefficient, so that
Denseer bed can be formed in very wide range, so the opereating specification of slurry bed system is wide, unit equipment production capacity is big, reaction
Device structure is simple, low cost；
Since the Pd catalyst granules in slurry bed system is smaller, there is good dispersibility, high activity and highly selective, because
The utilization rate of this catalyst in entire hydrogenation process is high, hydrogenation efficiency is high, in addition the dioxygen water partition coefficient in extraction process
Greatly, the concentration of extracted products is high, and mass fraction can achieve 40% or more；And due to the raising of selectivity, effective anthraquinone exists
Degradation in reaction process is fewer, and the catalyst content that device is disposably put into is relatively smaller, and uses and add successively, consumes volume
Low, operating cost is low.Therefore, anthraquinone hydrogenation can greatly improve the production of device using slurry bed process in Hydrogen Peroxide Production
Efficiency reduces catalyst and cycle working fluid dosage, reduces production cost.And since slurry bed process reacts anthraquinone hydrogenation
Uniformly, it avoids reaction process hot localised points from being formed and working solution is caused to be degraded, is conducive to the product quality for improving hydrogen peroxide.This
Outside, paste state bed reactor has relatively high space-time yield and hydrogenation selectivity, and reactor inner transmission matter is good, and heat transfer is uniform,
Catalyst is readily replaceable, the characteristics of particularly suitable for being mass produced.
US6306359 discloses the hydrogenation catalyst that a kind of slurry bed system prepares hydrogen peroxide, and catalyst is mainly by mass fraction
For 0.5-2.5% Pd, Pt or Rh as active component, metallic copper, silver or gold that mass fraction is 0.5-2.5% with
And the zirconium oxide that mass fraction is 4-6%, as catalyst promoter, content is the silica of 89-95% as catalyst carrier group
At above-mentioned catalyst is although can be improved the selectivity of anthraquinone hydrogenation, since above-mentioned catalyst is difficult to realize to noble metal
Effective dispersion of active component, causes the bullion content of catalyst higher, catalyst high expensive.US6126914 is disclosed
The preparation method of a kind of hydrogenation catalyst and hydrogenation catalyst, the catalyst are mainly suitable for using anthraquinone as working material system
The hydrogenation process of standby hydrogen peroxide；This hydrogenation catalyst mainly includes palladium and catalyst carrier, and carrier is mainly spherical silica,
And the scale of spheric granules for there are about mass fraction being 90% is 10-100um, the average grain diameter scale of silica sphere is
30-60um and Kong Rongwei 0.4-1.0ml/g.The catalyst shows relatively high activity, intensity, selectivity and stability.
However the method for preparing catalyst of the patent disclosure is mainly that the method for using deposition sedimentation prepares active component, is urged to improve
The palladium dispersion degree of agent, the basicity for the solution to be improved that is bound to, it is difficult to realize the high dispersive process of palladium catalyst active component.
In consideration of it, dispersion of the present invention for the noble metal active component of hydrogenation catalyst during anthraquinone hydrogenation, proposes
Using the silica of nitridation as carrier, hydrogenation catalyst by the principle of ion exchange is reached with amino and precious metal cation
The high dispersive feature of noble metal improves the activity and stability of hydrogenation catalyst；And by after to silica nitrogen treatment,
The property on surface is easy to the desorption of hydride, improves the selectivity of anthraquinone hydrogenation reaction, further increases the stability for adding hydrogen.
Summary of the invention:
For hydrogenation efficiency existing for existing slurry bed hydrogenation catalyst, low, the shortcoming of poor selectivity, of the invention
It is designed to provide a kind of high-dispersion loading type catalyst and preparation method thereof for anthraquinone hydrogenation production hydrogen peroxide, is improved single
The selectivity of Cheng Qing effect and effective anthraquinone, and further decrease the content of noble metal.The high-dispersion loading type prepared in the present invention
Slurry bed hydrogenation catalyst, with the amino group of controlled amounts on nitrogenous silica support, due to amino group be easy to
Precious metal ion carries out ion exchange, and the dispersion degree of noble metal can be improved, and reduces the particle scale of noble metal, improves catalyst
Hydrogenation activity and reduce noble metal usage amount；In addition, nitrogenous group introduces the property for changing silica support surface
Matter makes species among the hydrogenation being hydrogenated to be easy to be desorbed from catalytic inner, since anthraquinone hydrogenation reaction is a collection series connection
Integrated complex reaction is reacted in parallel, for effective anthraquinone and tetrahydro-anthraquinone, a step hydrogenation reaction is effectively to react,
Therefore, by introduce amino make intermediate hydride species be easy to be desorbed can be further improved plus hydrogen selectivity, effectively prevent
By-product largely generates, and improves the stability of hydrogenation catalyst, reduces the energy consumption of reaction.
In order to realize above-mentioned purpose of the invention, the present invention provides the following technical scheme that
The present invention provides a kind of slurry bed hydrogenation catalysts and its preparation method and application.
A kind of slurry bed hydrogenation catalyst, the catalyst include catalytic active component and catalyst carrier, in which:
The catalytic active component is selected from the combination of one or both of platinum-group noble metals Pd, Pt；Catalytic active component
Content in terms of precious metal simple substance, account for the 0.01-2.00wt% of total catalyst weight, in bimetallic combination, the content of Pd with
Simple substance meter accounts for the 50-100% of carrying metal total weight；
The carrier of the catalyst is nitrogenous silica support, and wherein the content of nitrogen accounts for the 0.1- of catalyst carrier weight
20%；
The Kong Rong of the catalyst carrier is less than 0.7cc/g.
Accounting for catalyst carrier weight by the nitrogen content after nitrogen treatment in the nitrogenous silica support is preferably
1-10wt%.
The nitrogenous silica support pattern is spherical shape, and the particle scale of carrier is 40-70 μm.
The Kong Rongwei of the nitrogenous silica support is not higher than 0.7cc/g, and the Kong Rong of preferred carrier is not higher than 0.55cc/
g。
First it is noted that nitrogen content in the carrier of the beaded catalyst, by the silica support of nitridation
Nitrogen content be 0.1-20%, nitrogen content therein not only influences the property on silica support surface, but also will affect catalysis
The active component dispersion degree of agent；It will be apparent that the content of silicon nitride is bigger, the amino group on surface is more, to cause carrier
Alkalinity it is stronger, since anthraquinone is a kind of species of electron, can make species anthrahydroquinone among the hydrogenation being hydrogenated to easy in this way
It is desorbed in from catalyst surface, improves the selectivity of anthraquinone hydrogenation.In addition, amino group increases, be easy to make NH- with it is expensive
The cation of metal swaps, so as to improve the dispersion degree of noble metal.Therefore, the nitrogen content that this patent requires is for carrying
The surface nature of body and the dispersion of noble metal have very important effect.However in theory, the nitrogen in silica contains
The higher the better for amount, however the nitrogen content of carrier needs high-temperature process that could improve, and high nitrogen content, which will increase, prepares catalyst
Energy consumption and material consumption, and low nitrogen content can reduce the performance of catalyst, it is therefore preferable that the nitrogen content of carrier is 1-10%.
The nitrogenous silica support pattern is spherical shape, and the particle scale of carrier is 40-70 μm；It is well known that spherical
The wear resistence and mechanical strength of catalyst granules are higher than the catalyst of other shapes, moreover, in order to preferably realize catalyst
The particle scale of fluidisation in gas-liquid-solid three-phase hydrogenation reaction, carrier cannot be greater than 120 μm, first greater than the particle of this scale
The external surface area that first will cause catalyst solid seriously reduces, to cause hydrogen and anthraquinone species in liquid-solid boundary
Mass transfer rate reduces, to reduce the reactivity for adding hydrogen.In addition, being bound to preferably fluidize the catalyst of bulky grain
The flow velocity for increasing gas, since reaction rate reduces, the amounts of hydrogen for reacting needs is reduced, and at this point, being urged to form solid
The fluidized state of agent increases hydrogen tolerance, and the effective rate of utilization for causing hydrogen reduces, to increase energy consumption and object
Consumption.Another aspect, reduce catalyst particle scale will increase liquid it is solid between mass transfer to improve plus the efficiency of hydrogen,
However the separation that will cause reaction liquid and solid catalyst in this way is difficult, increases the difficulty and cost of hydroprocessing.
The beaded catalyst is it is characterized by: the Kong Rong of the nitrogenous silica support is less than 0.7cc/g, preferably
The Kong Rong of carrier is less than 0.55cc/g；Anthraquinone hydrogenation reaction is the complex reaction process for integrating parallel connection and serial connection, choosing
Selecting property is particularly important for the stability and reduction energy consumption of catalyst and material consumption.Therefore, hydrogenation products anthrahydroquinone is improved from catalysis
Agent surface is rapidly desorbed, and seems most important for effective hydrogenation reaction.Hold relatively low carrier for hole, reacts
It is easy to be desorbed from catalyst surface in object, improves the selectivity of hydrogenation reaction；And for high Kong Rong, since substance is spread
It is relatively slow, reduce the selectivity of reaction；Therefore this preferred carrier hole, which holds, is less than 0.55cc/g.
A kind of the step of preparation method of slurry bed hydrogenation catalyst, method (one) prepares catalyst, is as follows:
It (1) is that 0.1-100H-1 is passed into oxidation with volume space velocity at 300-900 DEG C by the mixed gas containing nitrogen
Then silicon carrier bed passes through drying, and nitrogenize holding 1-36 hours；Obtain catalyst carrier A；
(2) the platinum-group noble metals active component is supported into above-mentioned steps 1) on obtained catalyst carrier A, pass through
Dry and roasting, is made oxidized catalyst B；
(3) the oxidized catalyst B of step 2) is restored, finally obtains catalyst C.
The nitrogenous gas of the step (1) is mainly one or two kinds of mixture of nitrogen, ammonia；The body of nitriding gas
Product flow velocity is preferably the 5-50H of the catalyst precursor either volume of silica support-1；Nitriding temperature is preferably 500-800
℃；Institute's nitridation time is preferably 5-24 hours.
A kind of the step of preparation method of slurry bed hydrogenation catalyst, method (two) prepares catalyst, is as follows:
(1) the platinum-group noble metals active component is supported on silica support, is then passed through at dry and roasting
Catalyst precursor A is obtained after reason；
(2) by the mixed gas containing nitrogen, ammonia either nitrogen and ammonia, at 300-900 DEG C, with volume space velocity
For 0.1-100H-1It is passed into the bed of catalyst precursor A and then passes through drying, and nitrogenize holding 1-36 hours；It is urged
Agent carrier B；
(3) the oxidized catalyst B of step (2) is restored, finally obtains catalyst C.
The volume flow rate of step (1) nitriding gas is preferably the volume of catalyst precursor either silica support
5-50H-1；Nitriding temperature is preferably 300-600 DEG C；Nitridation time is preferably 5-24 hours.
It supports described in the preparation method (one) and method (two) of the catalyst and is mainly supported by the method impregnated
Platinum-group noble metals presoma salt；The maturing temperature is that temperature is 150-750 DEG C, preferably 300-600 DEG C.
Restoring method mainly uses hydrogen to be restored in the preparation method (one) and method (two) of the catalyst, also
Former temperature is preferably 60-160 DEG C.
The precursor water solution of noble metal component described in the preparation method (one) and method (two) of the catalyst is main
For PdCl2、Pd(NO3)2、H2PdCl4、Na2PdCl4、Pd(acac)2、PtCl2、PtCl4、H2PtCl6One or both of with
On；
A kind of application of slurry bed hydrogenation catalyst, is mainly used in 2- ethyl hydrazine, 2- amyl anthraquinone, 2- tert-butyl
The either above-mentioned tetrahydro-anthraquinone catalytic hydrogenation of the mixture of anthraquinone, 2- vinyl anthraquinone and above-mentioned anthraquinone produces hydrogen peroxide
In.
Detailed description of the invention
The comparing result that Fig. 1 is plus hydrogen is evaluated.
Following embodiment will give further instruction to the present invention, but not thereby limiting the invention.
Embodiment 1
1) preparation of silica hydrogenation catalyst
The spherical silica powder 2g that particle scale is 200-400 mesh is weighed, above-mentioned powder is placed in pipe type calciner,
Then nitrogen treatment is carried out to silica support by following program.
A) it passes first into nitrogen and displacement 30min is carried out to the gas in roasting pipe, the oxygen in the tail gas of detection device contains
Amount is lower than 0.5%.
B) it is passed through nitrogen and ammonia gas mixture body that volume flow is 30ml/min, wherein the volumetric concentration of ammonia is
70%；
C) heating rate is used to be warming up to 750 DEG C for 5 DEG C/min, the silica for maintaining this temperature to be nitrogenized after r for 24 hours carries
Body；
D) palladium nitrate aqueous solution for configuring 2mg/ml, it is molten to be then added above-mentioned palladium nitrate into the silica support of nitridation
Liquid 5ml, then carries out 120 DEG C of dryings, and 350 DEG C of roasting 3hr obtain the palladium catalyst of oxidation state；
E) palladium catalyst of above-mentioned oxidation state is put into tube furnace, is passed through the hydrogen that volume flow is 30ml/min,
Required plus hydrogen palladium catalyst is obtained after restoring 5hr at being 80 DEG C in temperature.
The test method of nitrogen content mainly uses alkali fusion, particularly takes a certain amount of above-mentioned sample, mixes hydrogen-oxygen
It is uniform to change sodium either potassium hydroxide, being heated to temperature is 400 DEG C, and the ammonia of releasing is absorbed using sulfuric acid solution, is then used again
Boric acid carries out back titration, determines the nitrogen content containing silicon oxynitride by calculating the soda acid amount consumed in titration process.By
It is about 5.3% that silica after above procedure nitridation, which uses the nitrogen content of alkali fusion detection,.
The physical parameter characterization result of unformed silica and nitride-monox is as shown in table 1 below.
The comparison of the physical parameter of the unformed silica of table 1 and nitride-monox
| Project | Specific surface area m2/g | Hole holds cc/g | Average pore size nm |
| Embodiment 1 | 105 | 0.3 | 11.4 |
| Embodiment 2 | 230 | 0.86 | 15.0 |
| Embodiment 3 | 180 | 0.66 | 14.7 |
| Embodiment 4 | 87 | 0.27 | 12.4 |
| Embodiment 5 | 170 | 0.45 | 10.6 |
| Embodiment 6 | 207 | 0.78 | 15.1 |
| Embodiment 7 | 148 | 0.37 | 10.0 |
This time the evaluation of hydrogenation catalyst is mainly carried out using continuous mixed fluidized bed reactor.Evaluation uses in experiment
Working solution is the mixture of amyl anthraquinone and ethyl hydrazine, and solvent uses the mixture of heavy aromatics and diisobutyl carbinol (DIBC).Anti-
It answers and 2ml hydrogenation catalyst is added in device, adjusting mixing speed is 1200r/min, and the hydrogen flow rate of control is 20ml/min, work
The flow control of liquid is 120ml/hr, and the operating pressure control of system is 0.05MPa (gauge pressure), and the temperature control of hydrogenation reaction exists
40℃.Relevant plus hydrogen result is illustrated in fig. 1 shown below.
Embodiment 2
The preparation of silica hydrogenation catalyst
Using silica as the active component loading method class of the hydrogenation catalyst of carrier preparation and above-mentioned nitride-monox
Seemingly.Briefly, the palladium nitrate aqueous solution 20ml of 10mg/ml is configured, the spherical oxygen that particle scale is 200-400 mesh is then weighed
The palladium nitrate solution 5ml of above-mentioned configuration concentration is added in the silicon oxide powder of SiClx powder 2g, Xiang Shangshu, then carries out 120 DEG C and does
Dry, 350 DEG C of roasting 3hr obtain the palladium catalyst of oxidation state；The palladium catalyst of above-mentioned oxidation state is put into tube furnace, is passed through
Volume flow is the hydrogen of 30ml/min, obtain after reduction 5hr at being 80 DEG C in temperature plus hydrogen palladium catalyst.
The physical parameter of unformed silica is as shown in table 1.The comparing result for adding hydrogen to evaluate is as shown in Figure 1.
Embodiment 3
The preparation of silica hydrogenation catalyst
The step of preparation, is as described in embodiment 1；Other conditions are identical, the middle ammonia of nitrogen and ammonia gas mixture body it is dense
Degree is 10%, and nitridation time remains 1hr.Silica physical parameter after nitridation is as shown in table 1.
Silica nitrogen content after the nitridation measured by alkali fusion is 0.9%.The evaluation result of hydrogenation catalyst such as Fig. 1
It is shown.
Embodiment 4
The preparation of high nitrogen-containing nitride-monox hydrogenation catalyst
The step of preparation, is as described in embodiment 1；Other conditions are identical, this ammonification gas is pure ammonia, and is nitrogenized
Time remains r for 24 hours.Silica physical parameter after nitridation is as shown in table 1.
Silica nitrogen content after the nitridation measured by alkali fusion is 9.8%.The evaluation result of hydrogenation catalyst such as Fig. 1
It is shown.
Embodiment 5
The preparation of nitride-monox hydrogenation catalyst
The step of preparation, is as described in embodiment 2；Then other conditions are identical, and the program of nitridation is as follows:
A) it passes first into nitrogen and displacement 30min is carried out to the gas in roasting pipe, the oxygen in the tail gas of detection device contains
Amount is lower than 0.5%.
B) it is passed through nitrogen and ammonia gas mixture body that volume flow is 30ml/min, wherein the volumetric concentration of ammonia is
70%；
C) heating rate is used to be warming up to 450 DEG C for 5 DEG C/min, maintain that this temperature obtains titanium oxide after r for 24 hours plus hydrogen is urged
Agent；
D) palladium catalyst of above-mentioned oxidation state is put into tube furnace, is passed through the hydrogen that volume flow is 30ml/min,
Required plus hydrogen palladium catalyst is obtained after restoring 5hr at being 80 DEG C in temperature.
The physical parameter of the nitriding and oxidizing Si catalyst of oxidation state is as shown in table 1.
Silica nitrogen content after the nitridation measured by alkali fusion is 4.7%.The evaluation result of hydrogenation catalyst such as Fig. 1
It is shown.
Embodiment 6
The preparation of nitride-monox hydrogenation catalyst
The step of preparation, is as described in embodiment 5；
The physical parameter of the nitriding and oxidizing Si catalyst of oxidation state is as shown in table 1.Other conditions are identical, and nitrogen and ammonia are mixed
The concentration for closing the middle ammonia of gas is 10%, and nitriding temperature is adjusted to 300 degree, and nitridation time remains 1hr, adding after nitridation
Hydrogen catalyst physical parameter is as shown in table 1.
Silica nitrogen content after the nitridation measured by alkali fusion is 1.2%.The evaluation result of hydrogenation catalyst such as Fig. 1
It is shown.
Embodiment 7
The preparation of nitride-monox hydrogenation catalyst
The step of preparation, is as described in embodiment 5；Other conditions are identical, and the gas of nitridation is revised as pure ammonia, and nitrogenizes
Time remains r for 24 hours, and the hydrogenation catalyst physical parameter after nitridation is as shown in table 1.
Silica nitrogen content after the nitridation measured by alkali fusion is 10.5%.The evaluation result of hydrogenation catalyst is as schemed
Shown in 1.
From above example as can be seen that in the identical situation of active component palladium content, compared to pure silica plus hydrogen
The hydrogenation activity of catalyst, the silica hydrogenation catalyst (embodiment 1,3-7) after nitrogenizing is relatively high, this mainly due to
By the silica after nitridation, the amino group of carrier increases, and is easy to make the cationic Pd of NH- and noble metal2+, Pd
(H2O)2+It swaps, so as to improve the dispersion degree of noble metal, and then improves the activity of anthraquinone hydrogenation.However, working as nitrogen
When the nitrogen content of oxide/silica reduces (embodiment 3, embodiment 6), the activity of catalyst is relatively low.In addition, from Fig. 1
Can be seen that embodiment 1, the stability of the hydrogenation catalyst of 3-7 will be relatively higher than embodiment 2, this mainly due to
By the silica after nitridation, the alkalinity that the amino group on surface will cause carrier is stronger, since anthraquinone is a kind of to electricity
The species of son can make species anthrahydroquinone among the hydrogenation being hydrogenated to be easy to be desorbed from catalyst surface in this way, improve anthracene
Quinone adds the selectivity of hydrogen, to improve the stability of anthraquinone hydrogenation.However, if when the nitrogen content of catalyst is relatively low,
Such as embodiment 3 and 6, since catalyst surface does not have enough alkalinity, it is sufficient to allow plus hydrogen among species desorption, stability meeting
It reduces.
Claims (12)
1. a kind of slurry bed hydrogenation catalyst, it is characterised in that: the catalyst includes catalytic active component and catalyst carrier,
In:
The catalytic active component is selected from the combination of one or both of platinum-group noble metals Pd, Pt；Catalytic active component contains
Amount accounts for the 0.01-2.00wt% of total catalyst weight in terms of precious metal simple substance, and in bimetallic combination, the content of Pd is with simple substance
Meter, accounts for the 50-100% of carrying metal total weight；
The carrier of the catalyst is nitrogenous silica support, and wherein the content of nitrogen accounts for the 0.1- of catalyst carrier weight
20%；
The Kong Rong of the catalyst carrier is less than 0.7cc/g.
2. a kind of slurry bed hydrogenation catalyst described in accordance with the claim 1, it is characterised in that: the nitrogenous silica support
It is preferably 1-10wt% that the middle nitrogen content after nitrogen treatment, which accounts for catalyst carrier weight,.
3. a kind of slurry bed hydrogenation catalyst described in accordance with the claim 1, it is characterised in that: the nitrogenous silica support shape
Looks are spherical shape, and the particle scale of carrier is 40-70 μm.
4. a kind of slurry bed hydrogenation catalyst described in accordance with the claim 1, it is characterised in that: the nitrogenous silica support
Kong Rongwei is not higher than 0.7cc/g, and the Kong Rong of preferred carrier is not higher than 0.55cc/g.
5. a kind of a kind of preparation method of slurry bed hydrogenation catalyst as described in claim 1, it is characterised in that: this method packet
Include following step:
It (1) is 0.1-100H with volume space velocity at 300-900 DEG C by the mixed gas containing nitrogen-1It is passed into silica support
Then bed passes through drying, and nitrogenize holding 1-36 hours；Obtain catalyst carrier A；
(2) the platinum-group noble metals active component is supported into above-mentioned steps 1) on obtained catalyst carrier A, by drying
And roasting, oxidized catalyst B is made；
(3) the oxidized catalyst B of step (2) is restored, finally obtains catalyst C.
6. a kind of preparation method of slurry bed hydrogenation catalyst according to claim 5, it is characterised in that: the step
(1) nitrogenous gas is mainly one or two kinds of mixture of nitrogen, ammonia；The volume flow rate of nitriding gas is preferably catalyzed
The 5-50H of the agent presoma either volume of silica support-1；Nitriding temperature is preferably 500-800 DEG C；Institute's nitridation time is preferred
It is 5-24 hours.
7. a kind of a kind of preparation method of slurry bed hydrogenation catalyst as described in claim 1, it is characterised in that: this method packet
Include following step:
(1) the platinum-group noble metals active component is supported on silica support, then by dry and calcination process it
After obtain catalyst precursor A；
(2) it is with volume space velocity at 300-900 DEG C by the mixed gas containing nitrogen, ammonia either nitrogen and ammonia
0.1-100H-1It is passed into the bed of catalyst precursor A and then passes through drying, and nitrogenize holding 1-36 hours；It is catalyzed
Agent carrier B；
(3) the oxidized catalyst B of step (2) is restored, finally obtains catalyst C.
8. a kind of preparation method of slurry bed hydrogenation catalyst according to claim 7, it is characterised in that: the step
(1) volume flow rate of nitriding gas is preferably the 5-50H of the catalyst precursor either volume of silica support-1；Nitridation temperature
Preferably 300-600 DEG C of degree；Nitridation time is preferably 5-24 hours.
9. according to a kind of preparation method of slurry bed hydrogenation catalyst described in claim 5 or 7, it is characterised in that: the load
Load is that platinum-group noble metals presoma salt is supported by the method for dipping；The maturing temperature is 150-750 DEG C, preferably 300-
600℃。
10. according to a kind of preparation method of slurry bed hydrogenation catalyst described in claim 5 or 7, it is characterised in that: described to go back
Original method mainly uses hydrogen to be restored, and the temperature of reduction is preferably 60-160 DEG C.
11. according to a kind of preparation method of slurry bed hydrogenation catalyst described in claim 5 or 7, it is characterised in that: described expensive
The precursor water solution of metal component be mainly PdCl2, Pd (NO3) 2, H2PdCl4, Na2PdCl4, Pd (acac) 2, PtCl2,
One or more of PtCl4, H2PtCl6.
12. a kind of slurry bed hydrogenation catalyst described in accordance with the claim 1 prepares dioxygen hydration in slurry bed system anthraquinone hydrogenation
At middle application.
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| CN112973677A (en) * | 2019-12-13 | 2021-06-18 | 山西潞安矿业(集团)有限责任公司 | Preparation method and application of hydrophobic noble metal catalyst |
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