CN106391022A - Non-precious metal catalyst for preparing liquefied petroleum gas and preparation method of non-precious metal catalyst for preparing liquefied petroleum gas - Google Patents
Non-precious metal catalyst for preparing liquefied petroleum gas and preparation method of non-precious metal catalyst for preparing liquefied petroleum gas Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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Abstract
The invention discloses a non-precious metal catalyst for preparing synthesized liquefied petroleum gas and a preparation method of the non-precious metal catalyst. The non-precious metal catalyst comprises Ni, Cu and Hbeta molecular sieves. The preparation method includes preparing a mixed solution containing Cu and Ni, adding the mixed solution into Hbeta molecular sieve powder, performing stirring impregnation prior to ultrasonic impregnation, drying, roasting and forming so as to obtain the non-precious metal catalyst. The non-precious metal catalyst is applicable to the second stage of preparing the liquefied petroleum gas by a synthesis-gas two-step method and is high in selectivity and active stability as compared with a precious metal catalyst.
Description
Technical field
The present invention relates to one kind prepares liquefied petroleum gas catalyst and preparation method thereof from synthesis gas, it is particularly used for
Two sections of synthesis techniques prepare second segment during liquefied petroleum gas, that is, be used for non-precious metal catalyst and its preparation of dimethyl ether conversion
Method.
Background technology
Liquefied petroleum gas（LPG）It is the general name of propane and butane, containing a small amount of propylene, butylene, be environmentally friendly fuel, extensively
General for motor vehicles clean fuel, industrial, agriculture and home-use fuel, Chemical Manufacture raw material.At present, liquefied petroleum gas mainly comes
Come from the cracking gas in oil gas field associated gas and petroleum refining process.
Raw material needed for the fuel of world's consumption at present and Chemical Manufacture, depends on oil.In recent years due to oil
The increasingly minimizing of reserves and and crude oil external dependence degree continue to increase, and during utilization of energy for cause environmental pollution
Problem is increasingly taken seriously, and the fuel that search for oil alternative energy source develops novel environment friendly has caused countries in the world particularly to send out
Reach the common concern of country.
With economic rapid growth, the demand of the energy is also being continuously increased, for the country of rich coal, oil-poor, few gas
For, how coal or natural gas to be converted into high value-added product and make full use of the problem that coal resources are most attention,
Effectively utilizes natural gas and coal have boundless prospect, can bring huge economic benefit and social benefit.
Produce chemical products using coal or natural gas, generally require and first coal or natural gas are generated with water and oxygen reaction
Hydrogen and carbon monoxide are the gas of main component, are then passed through CO conversion and acid gas removal, by sulfur therein, nitrogen oxygen
Compound and carbon dioxide etc. remove, the ratio of adjustment hydrogen and CO, prepare synthesis gas.
The production technology of synthesis gas is ripe at present, and is widely used in methanol production industry.Raw material is made by synthesis gas,
Selective synthesis liquefied petroleum gas, is that natural gas and coal are changed into one of high value added product feasibility important technology, is
Produce the WeiLai Technology of high clean environmental protection fuel.
Gas renormalizing and coal gasification produce synthesis gas, and then synthesis gas is converted into the process of fluid product, is referred to as GTL
（Gas-to-Liquids）Technology.GTL commercial technologies route Related product has methanol, dimethyl ether and artificial oil.Although from conjunction
Gas production dimethyl ether and artificial oil is become to put into effect already, the catalyst producing methanol at present is to become most in GTL technology with technique
Ripe.
Producing the traditional method of Hydrocarbon by synthesis gas is F- T synthesis, refers to that CO is non-under solid catalyst effect
Homogeneous hydrogenation generates the hydro carbons of different chain length（C1-C25）Mixture and oxygenatedchemicalss.German Rule chemical company in 1936 the
A set of F-T artificial oil factory goes into operation, and mid-twentieth century develops rapidly because petroleum industry, so that F-T is synthesized and loses competitiveness.South Africa
Rich coal oil starvation, is subject to international community's politics and economic sanctions for a long time, is forced to continue development coal-to-oil industry, and achieves well to enter
Exhibition, South Africa Sasol company is coal liquifaction enterprise maximum in the world at present.The product of generally F- T synthesis is alkane, alkene and
Oxygenatedchemicalss, and Schulz-Anderson-Florry distribution is followed in the distribution of hydro carbons, so the hydrocarbon that F- T synthesis produce
Class compound needs to be used for fuel oil of motor-driven vehicle through processing, by-product hard waxes simultaneously.
The eighties in last century, the scientist of UCC synthesizes the molecular sieve of SAPO series, and wherein SAPO-34 generates second to methanol
Alkene and propylene have good selectivity, thus producing the MTO of the methanol production alkene with good prospect（Methanol to
Olefin）Technology.The nineties builds up the demonstration plant of 0.5 ton day in Norsk Hydro.The scientist C. D. of Mobil
Methanol dehydration is become hydrocarbon using ZSM-5 for catalyst by Chang, thus producing preparing gasoline by methanol MTG (Methanol to
Gasoline) technology.Mobile in 1986 are constructed and put into operation in New Zealand the gasoline apparatus producing 600000 tons per year.
MTO and MTG Technology is required for synthesizing methanol first, and methanol dehydration is carbon hydrocarbon compound afterwards, thus technique
Route is long.
With expanding economy, energy resource consumption is continuously increased, due to fuel oil and coal-fired produce oxysulfide, nitrogen oxides,
The air environmental pollution that dust etc. causes increases, thus, the continuous improvement of oil quality more strict to the quality standard of oil product
It is trend of the times, with the reinforcement of global environmental consciousness, Oil Refining Industry faces the heavy pressure of product quality upgrading all the time.Hydrogenation is de-
Sulfur denitrogenation Olefin decrease is only way.But the octane number of current gasoline is mainly derived from alkene and aromatic hydrocarbons, in order to ensure gasoline
Octane number, isomerization processes the main path being to improve octane number.The raising of gasoline product quality can increase oil refining process
Cost so that being possibly realized by the commercial applications of coal or natural gas synthetic liquid fuel.
Coal or natural gas are converted into synthesis gas, after purified treatment more transformed to adjust H2/ CO ratio produces synthesis
Gas, optionally synthesizing LPG with synthesis gas for unstripped gas is the effective way that coal or natural gas are converted into high added value fuel.
DME synthesis and two processes of dimethyl ether conversion are included by synthesis gas liquefied petroleum gas, each process is directed to
To catalyst.
Synthesis gas synthesis LPG has one-step method and two kinds of approach of two-step method, and one-step method used catalyst is by methanol synthesis catalyst
Agent and methanol dehydration catalyst are directly mixed to get, and required process route is short, but because methanol synthesis catalyst composition is generally
CuO-ZnO-Al2O3Catalyst, suitable reaction temperature is 220-280 DEG C, and molecular sieve its catalytic dehydration energy when higher than 300 DEG C
Power is just obvious.Therefore, in one-step technology, the suitable reaction temperature of two kinds of catalyst is different, does not reach excellent reaction effect
Really；Simultaneously because molecular sieve catalyst acidity is also easy to produce more by force carbon distribution, carbon distribution causes Dehydration of methanol to subtract after covering acid site
Weak, lead to CO conversion ratio and LPG selectivity to reduce.Two-step method synthesis liquefied petroleum gas technique in, first paragraph mainly generate with
Dimethyl ether is main intermediate product, and second segment is the nytron that dimethyl ether deoxidation hydro-conversion is based on propane and butane
Thing, the dimethyl ether that first paragraph generates need not separate with the mixture of water and be directly entered second segment reactor, first paragraph reaction temperature
Control at 260-280 DEG C, second segment reaction temperature controls at 340 DEG C -350 DEG C, two kinds of catalyst are all in each suitable anti-
Answer temperature range, reactivity worth integrally gets a promotion, extend the life-span of first paragraph dimethyl ether synthetic catalyst, and catalyst
Regeneration easily, therefore not only CO high conversion rate and also catalyst stability is good.Therefore two-step method synthesis liquefied petroleum gas technique is excellent
In one-step method.
CN1054202A discloses a kind of catalyst being produced propane or liquefied petroleum gas by synthesis gas, and catalyst is by methanol
Synthetic catalyst Cu-Zn/Al2O3(or Cu-Zn/Cr2O3) with superheated vapor process HY catalyst mixed grinding make.In
Pressure（2-4MPa）, CO conversion ratio reaches 64% under 260-320 DEG C of reaction condition, produces propane or liquefied petroleum with high selectivity
Gas.The method adopts one-step method, and catalyst can not operate under optimal reaction temperature, and catalyst is difficult to regenerate, by-product simultaneously
CO2More with the amount of methane, catalyst is relatively costly.
CN101016494A discloses one kind from the carbon raw material gas such as natural gas via synthesis gas, methanol or dimethyl ether manufacture
The method of liquefied petroleum gas.First from carbon raw material producing synthesis gas, then manufacture crude carbinol or dimethyl ether, Ran Hou from synthesis gas
In the presence of catalyst for producing liquefied petroleum gas agent, so that prepared crude carbinol or dimethyl ether and hydrogen is reacted, be obtained with propane and fourth
Liquefied petroleum gas based on alkane.In the method, catalyst for producing liquefied petroleum gas agent uses precious metals pd/ZSM-5 catalysis
Agent, preparation cost is high.
Content of the invention
In order to overcome the shortcomings of the prior art, the invention provides a kind of non-noble preparing liquefied petroleum gas
Metallic catalyst and preparation method thereof, the second segment in particular for being prepared by synthesis gas two-step method during liquefied petroleum gas is used for turning
Change catalyst of dimethyl ether and preparation method thereof.The second segment that synthesis gas two-step method is prepared during liquefied petroleum gas adopts this catalyst
When, liquefied petroleum gas selectivity is high, and activity stability is good.
The non-precious metal catalyst of the synthesis liquefied petroleum gas that the present invention provides, consisting of：Ni and Cu and H beta molecule
Sieve, the wherein total mass fraction of Ni and Cu are 5.0%-20.0%, preferably 9.0%-20.0%, Ni：The mass ratio of Cu is 1:0.9-
1:1.1, remaining is H beta-molecular sieve.
The non-precious metal catalyst of the synthesis liquefied petroleum gas that the present invention provides, is preferably as follows：The gross mass of Ni and Cu is divided
Number is 10.0%, Ni：The mass ratio of Cu is 1:1.
In the non-precious metal catalyst of synthesis liquefied petroleum gas that the present invention provides, the SiO of H beta-molecular sieve2/Al2O3Mole
Than for 15-50, preferably 25.
The preparation method of the non-precious metal catalyst of synthesis liquefied petroleum gas that the present invention provides, including：
（1）Prepare the mixed solution containing Cu and Ni；
（2）By step（1）The mixed solution of gained is added in H beta-molecular sieve powder, in 50-60 DEG C of stirring dipping 2-6h, then enters
Row ultrasonic Treatment impregnates, and then drying, roasting and molding is obtained catalyst.
Step（1）In, in the mixed solution containing Cu and Ni, Ni concentration 0.30mol/L-1.2mol/L, Cu concentration is
0.28mol/L-1.12mol/L.
Step（2）In, the frequency of described ultrasound wave is 22kHz-42kHz, preferably 32kHz-42kHz, supersound process
Time is 2h-3h.
Step（2）In, by step（1）The mixed solution of gained is added in H beta-molecular sieve powder, wherein H beta-molecular sieve powder
End and step（1）The mass ratio of the mixed solution of gained is 1:1.3-1:1.5.
Step（2）In, the drying of described catalyst and roasting condition as follows：3-15h is dried under the conditions of 80-120 DEG C,
Roasting 2-6h under the conditions of 450-600 DEG C.
Step（2）In, described shaping of catalyst can be carried out using conventional method, such as compression molding method.
Compared with prior art, the invention has the advantages that：
（1）Precious metals pd is substituted using Ni-Cu base metal and has greatly saved catalyst cost, and reached and adopt precious metals pd
Reaction effect during catalyst, even better than precious metals pd catalyst, and reduce the selectivity of byproduct methane.Additionally,
Metal Pd has the shortcomings of easy poisoning and deactivation, stability difference.Precious metals pd is substituted using Ni-Cu bimetallic and can also improve catalysis
Agent stability, makes commercial production liquefied petroleum gas be more feasible；
（2）In non-precious metal catalyst preparation process of the present invention, active metal can be promoted equal on a catalyst using ultrasound wave
Even dispersion, increasing active component permeability makes active component be fully contacted with molecular sieve, adjusts Ni, Cu ion in molecular sieve pores
With the distribution in cage, such that it is able to the acidity of Molecular regulator sieve, improve LPG selectivity, reduce the generation of by-product, especially
It is C5 +Heavy constituent hydrocarbon, also can slow down carbon distribution.
Brief description
Fig. 1 is two-step method liquefied petroleum gas process chart；
Wherein reference is as follows：I-DME synthesis reactor, II-dimethyl ether conversion reactor, 1- separator；
Fig. 2 carries out the reaction result of stability experiment for the present invention using the 5%Ni-5%Cu/ beta-molecular sieve catalyst of embodiment 3.
Specific embodiment
Enter by the following examples and the present invention is described in detail, but the invention is not restricted to these embodiments.
As shown in figure 1, the technological process that two reactor series connection prepares liquefied petroleum gas by synthesis gas is as follows, synthesis gas enters
Enter first paragraph DME synthesis reactor I reacted after, generate the mixture of dimethyl ether and water, then immediately proceed to second segment two
Methyl ether conversion reactor II is reacted, and the product obtaining enters the separated rear acquisition product LPG of separator 1.
The embodiment of the present invention and comparative example carry out activity rating using two reactor series connection to catalyst, as shown in figure 1,
Respectively by dimethyl ether synthetic catalyst and dimethyl ether conversion Catalyst packing in internal diameter in the tubular fixed-bed reactor of 6mm,
Catalyst particle size 20-40 mesh.Catalyst using front need reduce, with containing 5v%H2-95v%N2Gaseous mixture at ambient pressure also
Former 4h, first paragraph reduction temperature and second segment reduction temperature are 300 DEG C, and reduction is down to room temperature after terminating.
Mole composition of the synthesis gas that the embodiment of the present invention and comparative example are adopted is as follows：Ar 3%, CO 24%, CO28%,
H265%.
The embodiment of the present invention and comparative example carry out in evaluation procedure to catalyst, and the reaction condition that first paragraph is adopted is such as
Under：Reaction pressure 4MPa, gas space velocity 2500h-1, 275 DEG C of one section of reaction temperature；The reaction condition that second segment is adopted is as follows：
Reaction pressure 4MPa, gas space velocity 2500h-1, 350 DEG C of second-stage reaction temperature.
Embodiment 1
Weigh 12.3871gNi (NO3)2 .6H2O, 9.5043gCu (NO3)2 .3H2O, addition 70mL deionized water, stirring and dissolving, separately
Weigh 50gSiO2/Al2O3Mol ratio is that 25 H beta-molecular sieve is placed in beaker, and the solution preparing is slowly added in beaker, with
When be stirred continuously.Stirring dipping 3h in 50 DEG C of waters bath with thermostatic control, introduces ultrasound wave dipping 3h, ultrasonic frequency 22kHz, leaching afterwards
The good catalyst of stain is put in baking oven and 4h is dried in 120 DEG C, finally in 450 DEG C of roasting 4h, takes 20-40 through tabletting, broken, screening
Mesh.
Activity rating is carried out to catalyst using two reactor series connection.By industrial methanol synthetic catalyst and γ-Al2O3
Broken, screening takes 20-40 mesh, respectively weighs 0.5g mix homogeneously and loads first paragraph reactor；Weigh 1g catalyst and load second segment
Reactor.First paragraph catalyst adopts Cu-Zn-Al2O3/γ-Al2O3Mixed catalyst, wherein Cu-Zn-Al2O3Catalyst is business
Use catalyst C207.After evaluation, product is introduced gas chromatogram on-line analyses.
Reaction result under this kind of state is designated as Cat1, is specifically shown in Tables 1 and 2.
Embodiment 2
Specific implementation process is roughly the same with embodiment 1, is that ultrasonic frequency is 32kHz in place of difference.
Reaction result under this kind of state is designated as Cat2, is specifically shown in Tables 1 and 2.
Embodiment 3
Specific implementation process is roughly the same with embodiment 1, is that ultrasonic frequency is 42kHz in place of difference.
Reaction result under this kind of state is designated as Cat3, is specifically shown in Tables 1 and 2.
Embodiment 4
Specific implementation process is roughly the same with embodiment 1, is that ultrasonic frequency is 42kHz in place of difference, 50 DEG C of waters bath with thermostatic control
Middle stirring dipping 4h, ultrasound wave impregnates 2h.
Catalyst reaction result under this kind of state is designated as Cat4.
Embodiment 5
Specific implementation process is roughly the same with embodiment 3, is to impregnate Ni (NO in place of difference3)2 .6H2The quality of O is
6.1936g, Cu (NO3)2 .3H2The quality of O is 4.7522g.
Catalyst reaction result under this kind of state is designated as Cat5.
Embodiment 6
Specific implementation process is roughly the same with embodiment 3, is to impregnate Ni (NO in place of difference3)2 .6H2The quality of O is
24.7742g, Cu (NO3)2 .3H2The quality of O is 19.0086g.
Catalyst reaction result under this kind of state is designated as Cat6.
Comparative example 1
Specific implementation process is roughly the same with embodiment 3, and difference is only stirring dipping 6h in 50 DEG C of waters bath with thermostatic control, is not introduced into
Ultrasound wave dipping process.
Catalyst reaction result under this kind of state is designated as DCat1, is specifically shown in Tables 1 and 2.
Comparative example 2
Specific implementation process is roughly the same with embodiment 3, is that ultrasonic frequency is 52 kHz in place of difference.
Catalyst reaction result under this kind of state is designated as DCat2, is specifically shown in Tables 1 and 2.
Comparative example 3
Specific implementation process is roughly the same with embodiment 3, is stirring dipping 5.5h in 50 DEG C of waters bath with thermostatic control in place of difference, ultrasonic
Ripple impregnates 0.5h.
Catalyst reaction result under this kind of state is designated as DCat3, is specifically shown in Tables 1 and 2.
Comparative example 4
With the PdCl having configured2As Pd source, the mass concentration of palladium chloride solution is 0.1033g/mL to solution, is measured with graduated cylinder
0.4165g palladium chloride solution is placed in beaker, adds appropriate deionized water to be configured to 70mL Palladous chloride. weak solution, by 50gH β
Molecular sieve（With embodiment 1）It is added in the Palladous chloride. weak solution having configured, add molecular sieve to stir, make pulpous state
Suspension, then suspension is placed in constant temperature blender with magnetic force and is stirred impregnating, dipping temperature is 50 DEG C, dip time 6
Hour, catalyst impregnate is evaporated on Rotary Evaporators, is moved in baking oven drying 4 at 120 DEG C after being evaporated little
When.Prepare the formalin that mass concentration is 1% in advance, dried molecular sieve catalyst is placed in appropriate formalin
Soak 2 hours, the effect soaking formalin is the chloride ion removing on catalyst, is filtered catalyst afterwards, uses
Deionized water rinsing two or three times, catalyst is placed on Rotary Evaporators is dried again, and dried catalyst is put into baking
8 hours are dried in case at 120 DEG C, finally dried catalyst are put in Muffle furnace 4 hours systems of roasting at 450 DEG C
Become 0.5%Pd/ beta catalyst.
Catalyst reaction result under this kind of state is designated as DCat4, is specifically shown in Tables 1 and 2.
Stability test
First paragraph catalyst with embodiment 1, that is, by Cu-ZnO-Al2O3Catalst for synthesis of methanol and γ-Al2O3Composition, by quality
Than for 1:1 granule mixing, second segment catalyst is 5%Ni-5%Cu/ beta-molecular sieve catalyst with embodiment 3, and reaction carries out 100
Hour.First paragraph initial reaction temperature is 273 DEG C, and after reaction 70 hours, temperature brings up to 277 DEG C to keep CO conversion ratio, second
Section reaction temperature is constantly maintained at 350 DEG C, reaction pressure 4MPa, synthesis gas air speed 2500mL/h g.See Fig. 2.
The each embodiment of table 1 and the evaluation result of comparative example catalyst
| Ultrasonic frequency, kHz | Ultrasonic time, h | The content of Ni, wt% | The content of Cu, wt% | XCO, % | S-CO2, % | S-LPG, wt% | Y-HC, % | |
| Cat1 | 22 | 3 | 5 | 5 | 77.91 | 24.59 | 74.55 | 58.75 |
| Cat2 | 32 | 3 | 5 | 5 | 79.13 | 23.41 | 78.32 | 60.60 |
| Cat3 | 42 | 3 | 5 | 5 | 80.58 | 23.37 | 79.14 | 61.75 |
| Cat4 | 42 | 2 | 5 | 5 | 78.98 | 24.08 | 79.05 | 59.96 |
| Cat5 | 42 | 3 | 2.5 | 2.5 | 77.91 | 25.57 | 73.85 | 57.98 |
| Cat6 | 42 | 3 | 10 | 10 | 78.03 | 24.77 | 76.62 | 58.70 |
| DCat1 | -- | -- | 5 | 5 | 76.50 | 24.70 | 75.75 | 57.60 |
| DCat2 | 52 | 3 | 5 | 5 | 79.56 | 25.83 | 69.98 | 59.01 |
| DCat3 | 42 | 0.5 | 5 | 5 | 80.35 | 26.39 | 70.83 | 59.14 |
| DCat4 | -- | -- | -- | -- | 84.49 | 22.23 | 73.14 | 65.70 |
Note: XCOCO conversion ratio, %（Molar fraction）
S-LPG LPG selectivity, %（Mass fraction）
S-CO2—CO2Selectivity, %（Molar fraction）
Y-HC hydrocarbon productivity, %（Molar fraction）
Hydrocarbon distribution (wt %) in each embodiment of table 2 and comparative example products therefrom
| C1 | C2 | C3 | C4 | C5 | C6 + | |
| Cat1 | 2.94 | 6.82 | 29.67 | 44.87 | 13.67 | 2.03 |
| Cat2 | 3.59 | 11.47 | 35.80 | 42.53 | 6.62 | 0.08 |
| Cat3 | 3.38 | 10.89 | 38.24 | 40.91 | 6.58 | 0.12 |
| Cat4 | 2.77 | 11.47 | 37.82 | 41.23 | 6.60 | 0.11 |
| Cat5 | 3.94 | 10.59 | 29.37 | 44.48 | 11.43 | 0.19 |
| Cat6 | 5.15 | 11.21 | 38.70 | 37.92 | 6.93 | 0.09 |
| DCat1 | 2.61 | 7.50 | 24.76 | 49.30 | 13.77 | 2.05 |
| DCat2 | 3.21 | 6.47 | 29.18 | 40.80 | 11.66 | 8.68 |
| DCat3 | 2.67 | 7.32 | 24.67 | 46.17 | 16.06 | 3.12 |
| DCat4 | 5.19 | 4.11 | 29.14 | 44.00 | 12.05 | 5.51 |
Claims (9)
1. a kind of non-precious metal catalyst of synthesis liquefied petroleum gas, consisting of：Ni and Cu and H beta-molecular sieve, wherein Ni and
The total mass fraction of Cu is 5.0%-20.0%, preferably 9.0%-20.0%, Ni：The mass ratio of Cu is 1:0.9-1:1.1, remaining is
H beta-molecular sieve.
2. catalyst according to claim 1 it is characterised in that：The total mass fraction of Ni and Cu is 10.0%, Ni：Cu's
Mass ratio is 1:1.
3. catalyst according to claim 1 it is characterised in that：The SiO of H beta-molecular sieve2/Al2O3Mol ratio is 15-50,
It is preferably 25.
4. the preparation method of the arbitrary described catalyst of claim 1 ~ 3, including：
（1）Prepare the mixed solution containing Cu and Ni；
（2）By step（1）The mixed solution of gained is added in H beta-molecular sieve powder, impregnates 2-6h in 50-60 DEG C of stirring, then
Carry out ultrasonic Treatment dipping, then drying, roasting and molding is obtained catalyst.
5. method according to claim 4 it is characterised in that：Step（1）In, in the mixed solution containing Cu and Ni, Ni is dense
Degree 0.30mol/L-1.2mol/L, Cu concentration is 0.28mol/L-1.12mol/L.
6. method according to claim 4 it is characterised in that：Step（2）In, the frequency of described ultrasound wave is 22kHz-
42kHz, preferably 32kHz-42kHz, sonication treatment time is 2h-3h.
7. method according to claim 4 it is characterised in that：Step（2）In, by step（1）The mixed solution of gained adds
Enter in H beta-molecular sieve powder, wherein H beta-molecular sieve powder and step（1）The mass ratio of the mixed solution of gained is 1:1.3-1:
1.5.
8. method according to claim 4 it is characterised in that：Step（2）In, the drying of described catalyst and roasting condition
As follows：3-15h is dried under the conditions of 80-120 DEG C, roasting 2-6h under the conditions of 450-600 DEG C.
9. method according to claim 4 it is characterised in that：Step（2）In, described shaping of catalyst adopts compression molding
Method.
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|---|---|---|---|---|
| CN106861751A (en) * | 2017-02-16 | 2017-06-20 | 浙江科技学院 | The preparation method and product of the nucleocapsid catalyst containing H beta-molecular sieves and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861751A (en) * | 2017-02-16 | 2017-06-20 | 浙江科技学院 | The preparation method and product of the nucleocapsid catalyst containing H beta-molecular sieves and application |
| CN106861751B (en) * | 2017-02-16 | 2019-10-15 | 浙江科技学院 | The preparation method and product of the nucleocapsid catalyst of the beta-molecular sieve containing H and application |
| CN110280303A (en) * | 2019-05-21 | 2019-09-27 | 北京高新利华科技股份有限公司 | A kind of catalyst and preparation method thereof preparing liquefied petroleum gas from synthesis gas |
| CN110280303B (en) * | 2019-05-21 | 2022-05-17 | 北京高新利华科技股份有限公司 | Catalyst for preparing liquefied petroleum gas from synthesis gas and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106391022B (en) | 2019-03-19 |
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