CN106732760B - A kind of synthesis gas prepares catalyst of liquefied petroleum gas and preparation method thereof - Google Patents
A kind of synthesis gas prepares catalyst of liquefied petroleum gas and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 239000003915 liquefied petroleum gas Substances 0.000 title claims abstract description 31
- 239000007789 gas Substances 0.000 title claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 36
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 4
- 238000005470 impregnation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 3
- 101150019148 Slc7a3 gene Proteins 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910005183 Ga(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 propylene, butylene Chemical group 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- 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
- C10L3/12—Liquefied petroleum gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the catalyst and preparation method thereof that a kind of synthesis gas prepares liquefied petroleum gas.The composition of the catalyst are as follows: Ni, Cu, auxiliary agent and H- beta-molecular sieve, wherein auxiliary agent is Ca, Ga and La, on the basis of the weight of catalyst, the total mass fraction 5.0%-20.0% of Ni and Cu, the content of auxiliary agent is 0.1%-3.0% in mass, remaining is H- beta-molecular sieve；Wherein the mass ratio of auxiliary agent Ca, Ga and La is 1-10:1:1-10, and the mass ratio of Ni:Cu is 1:0.8-1:1.5.The catalyst is suitable for second segment when synthesis gas two-step method prepares liquefied petroleum gas, and CO can be greatly lowered2Selectivity, improve the selectivity of liquefied petroleum gas, the stability of catalyst is preferable.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof that liquefied petroleum gas is prepared from synthesis gas, specifically use
Second segment when two step synthesis technologies prepare liquefied petroleum gas is used for the composite metal catalyst and its system of dimethyl ether conversion
Preparation Method.
Background technique
With the development of petro chemical industry, liquefied petroleum gas (LPG) is used as a kind of chemical industry base stock and New-type fuel,
It is more and more valued by people.Its main component is propane and butane, additionally contains a small amount of propylene, butylene, is environment friend
Good type fuel, it is easy for operation because of its calorific value height, smoke dust, without breeze, widely enter people's lives field, such as
For motor vehicle clean fuel, industry, agricultural and home-use fuel.In addition, liquefied petroleum gas is also used to cut metal, it to be used for agriculture
Baking and the roasting of Industrial Stoves of product etc..Currently, liquefied petroleum gas is mainly derived from oil gas field associated gas and petroleum refining
Cracking gas in the process, yield have been unable to meet ever-increasing market demand, need to develop new technique.
CN1054202A discloses a kind of catalyst that propane or liquefied petroleum gas are produced by synthesis gas, and catalyst is by methanol
Synthetic catalyst Cu-Zn/Al2O3(or Cu-Zn/Cr2O3) with superheated vapor processing H-Y catalyst mixed grinding be made.In
Pressure (2-4MPa), CO conversion ratio, which reaches 64%, under 260-320 DEG C of reaction condition, highly selective (propane account for hydro carbons 96%) makes
Take propane or liquefied petroleum gas.This method uses one-step method, and catalyst cannot operate under optimal reaction temperature, and catalyst is not easy
Regeneration, while by-product CO2Amount it is more, and hydro carbons only accounts for 33.62% in product.
Carbon dioxide is generated as a kind of by-product in the reaction, is a kind of public hazards substance, is the main tribute of greenhouse effects
Contributor, in past 100 years, the concentration of carbon dioxide increases to 350ppm, Global Temperature by 270-275ppm in atmosphere
0.6 DEG C is increased, the increasing of weather will be warm to generate tremendous influence to the mankind.Therefore, the content of carbon dioxide in product is reduced not
Greenhouse effects can only be alleviated, the yield of hydrocarbon can also be increased, be of great significance for preparing liquefied petroleum gas, it can be in the future
Industrialization reduces cost, increases benefit.
Summary of the invention
In order to make up shortcoming in the prior art, the present invention provides a kind of synthesis gas to prepare urging for liquefied petroleum gas
Agent and preparation method thereof is mainly used for second segment when preparing liquefied petroleum gas by synthesis gas two-step method for converting diformazan
Catalyst of ether and preparation method thereof.Catalyst degradation CO2Selectivity, and improve liquefied petroleum gas selectivity, urge
The stability of agent is preferable.
Synthesis gas provided by the invention prepares the catalyst of liquefied petroleum gas, consisting of: Ni, Cu, auxiliary agent and H- β points
Son sieve, wherein auxiliary agent be Ca, Ga and La, the total mass fraction 5.0%-20.0% of Ni and Cu, preferably 9.0%-15.0%, auxiliary agent
Content is 0.1%-3.0% in mass, preferably 0.3%-2.5%, remaining is H- beta-molecular sieve；The wherein matter of auxiliary agent Ca, Ga and La
For amount than being 1-10:1:1-10, the mass ratio of preferably 1-5:1:2-8, Ni:Cu are 1:0.8-1:1.5.
Synthesis gas provided by the invention prepares the catalyst of liquefied petroleum gas, preferably as follows: using the weight of catalyst as base
Standard, the content of Ni are 1.0%-10.0%, and the content of Cu is 1.0%-10.0%, and the content of auxiliary agent is 0.3%-2.5%, Ca, Ga and La
Mass ratio be 1-5:1:2-8.
Synthesis gas provided by the invention is prepared in the catalyst of liquefied petroleum gas, and the Si/Al molar ratio of H- beta-molecular sieve is
15-50, preferably 20-30.
Synthesis gas provided by the invention prepares the preparation method of the catalyst of liquefied petroleum gas, comprising:
(1) mixed solution containing Cu, Ni and auxiliary agent Ca, Ga, La is prepared；
(2) step (1) resulting mixed solution is added in H- beta-molecular sieve powder, is impregnated, dry and roasting obtains
To the catalyst.
In step (1), in the mixed solution containing Cu, Ni and auxiliary agent, Ni concentration 0.60-0.70mol/L, Cu concentration is
The concentration of 0.55-0.65mol/L, Ca are 0.02-0.2mol/L, and the concentration of Ga is 0.02-0.2mol/L, and the concentration of La is
0.02-0.2mol/L。
In step (2), step (1) resulting mixed solution is added in H- beta-molecular sieve powder, wherein H- beta-molecular sieve
The mass ratio of powder and step (1) resulting mixed solution is 1:1.3-1:1.5.
In step (2), the dipping be under 50-60 DEG C of stirring condition dipping 4 ~ 8h, the drying of the catalyst and
Roasting condition is as follows: dry 8-12h under the conditions of 110-130 DEG C roasts 2-6h under the conditions of 400 DEG C -600 DEG C.
In step (2), the catalyst can also through forming, molding can using conventional method carry out, such as tabletting at
Type method.
Catalyst of the invention prepares the application in liquefied petroleum gas in synthesis gas, especially in two-step method synthesis gas liquid
Application in the second segment of liquefied oil gas technique produces liquefied petroleum gas for dimethyl ether conversion.
Compared with prior art, the present invention has the advantage that
Synthesis gas of the invention prepares the catalyst of liquefied petroleum gas, uses Ni and Cu for main active component, H- beta molecule
Sieve is carrier component, and Ca, Ga and La can be improved the stability of catalyst by the mutual cooperation of each component for adjuvant component,
And CO is greatly lowered2Selectivity, be conducive to the generation of hydrocarbon.
Detailed description of the invention
Fig. 1 is two-step method liquefied petroleum gas process flow chart；
Wherein appended drawing reference is as follows: I-DME synthesis reactor, II-dimethyl ether conversion reactor, III-drainer；
Fig. 2 is the 5%Ni-5%Cu-0.25%Ca-0.1%Ga-0.5%La/ beta-molecular sieve catalyst that the present invention uses embodiment 1
Carry out the reaction result of stability experiment.
Specific embodiment
The present invention is described in detail by the following examples, but the present invention is not limited to these Examples.
The process flow that two reactor series connection prepares liquefied petroleum gas by synthesis gas as shown in Figure 1: is as follows: synthesis gas into
Enter first segment DME synthesis reactor I it is reacted after, generate the mixture of dimethyl ether, methanol and water, then immediately proceed to the
Two sections of dimethyl ether conversion reactor II are reacted, and are made water condensation through drainer III, are finally obtained C1-C6Mixed gas, discoloration
Spectrum carries out on-line checking.
The embodiment of the present invention and comparative example are all made of two reactor series connection and carry out activity rating to catalyst, such as Fig. 1 institute
Show, respectively by dimethyl ether synthetic catalyst and dimethyl ether conversion Catalyst packing in the tubular fixed-bed reactor that internal diameter is 6mm
In, catalyst particle size 20-40 mesh.Catalyst is using preceding needing to restore, with containing 5v%H2-95v%N2Gaseous mixture under normal pressure
4h is restored, first segment reduction temperature and second segment reduction temperature are 300 DEG C, and room temperature is down to after reduction.
Mole composition of synthesis gas used by the embodiment of the present invention and comparative example is as follows: Ar 2.83%, CO 23.5%,
CO27.76%, H2 65.91%。
The embodiment of the present invention and comparative example carry out in evaluation procedure catalyst, and reaction condition used by first segment is such as
Under: reaction pressure 4MPa, gas space velocity 2500h-1, one section 275 DEG C of reaction temperature；Reaction condition used by second segment is as follows:
Reaction pressure 4MPa, gas space velocity 2500h-1, 350 DEG C of second-stage reaction temperature.
Embodiment 1
Weigh 2.4767gNi (NO3)2 .6H2O, 1.9012gCu (NO3)2 .3H2O, 0.1476gCa (NO3)2 .4H2O,
0.0300g Ga(NO3)3 .9H2O and 0.7800gLa (NO3)3 .6H214mL deionized water is added in O, and stirring and dissolving separately weighs
The H- beta-molecular sieve that 10gSi/Al molar ratio is 25 is placed in eggplant type bottle, the solution prepared is slowly added in eggplant type bottle, while not
Disconnected stirring.The stirring dipping 6h in 60 DEG C of waters bath with thermostatic control, then impregnated catalyst is put into baking oven in 120 DEG C of dry 8h,
Finally in 450 DEG C of roasting 4h, 20-40 mesh is taken through tabletting, broken, screening, obtains catalyst A, composition is shown in Table 1.
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 and is uniformly mixed loading first segment reactor；It weighs 1g catalyst A and is packed into second segment
Reactor.First segment catalyst uses Cu-Zn-Al2O3/γ-Al2O3Mixed catalyst, wherein Cu-Zn-Al2O3Catalyst is quotient
With catalyst C207.After evaluation, product is introduced into gas-chromatography on-line analysis.
Reaction result under such state is denoted as Cat1, is specifically shown in Table 2 and table 3.
Embodiment 2
Specific implementation process is roughly the same with embodiment 1, and difference place is that Ca with La content is different, obtains catalyst B,
Composition is shown in Table 1.
Activity rating method is carried out with embodiment 1 to catalyst using two reactor series connection, difference is that second segment is urged
Agent is catalyst B.
Reaction result under such state is denoted as Cat2, is specifically shown in Table 2 and table 3.
Embodiment 3
Specific implementation process is roughly the same with embodiment 1, and difference place is that La content is different, obtains catalyst C, forms
It is shown in Table 1.
Activity rating method is carried out with embodiment 1 to catalyst using two reactor series connection, difference is that second segment is urged
Agent is catalyst C.
Catalyst reaction result under such state is denoted as Cat3.Specifically it is shown in Table 2 and table 3.
Embodiment 4
Specific implementation process is roughly the same with embodiment 1, and difference place is that Ca with La content is different, obtains catalyst D,
Composition is shown in Table 1.
Activity rating method is carried out with embodiment 1 to catalyst using two reactor series connection, difference is that second segment is urged
Agent is catalyst D.
Catalyst reaction result under such state is denoted as Cat4.Specifically it is shown in Table 2 and table 3.
Embodiment 5
Specific implementation process is roughly the same with embodiment 1, and difference is that Ca with La content is different, obtains catalyst E, forms
It is shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst F.
Catalyst reaction result under kind state is denoted as Cat5, is specifically shown in Table 2 and table 3.
Embodiment 6
Specific implementation process is same as Example 1, and difference is that Ca content is different, obtains catalyst F, and composition is shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst F.
Catalyst reaction result under such state is denoted as Cat6, is specifically shown in Table 2 and table 3.
Embodiment 7
Specific implementation process is roughly the same with embodiment 1, and difference is that Ca with Ga content is different, obtains catalyst G, forms
It is shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst G.
Catalyst reaction result under such state is denoted as Cat7, is specifically shown in Table 2 and table 3.
Embodiment 8
Specific implementation process is roughly the same with embodiment 1, and difference is that Ca with Ga content is different, obtains catalyst H, forms
It is shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst H.
Catalyst reaction result under such state is denoted as Cat8, is specifically shown in Table 2 and table 3.
Embodiment 9
Specific implementation process is roughly the same with embodiment 1, and difference is that Cu, Ca, Ga are different with La content, obtains catalyst
I, composition are shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst I.
Catalyst reaction result under such state is denoted as Cat9, is specifically shown in Table 2 and table 3.
Embodiment 10
Specific implementation process is roughly the same with embodiment 1, and difference is that Ni with Ga content is different, obtains catalyst J, forms
It is shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst J.
Catalyst reaction result under such state is denoted as Cat10, is specifically shown in Table 2 and table 3.
Comparative example 1
Specific implementation process is roughly the same with embodiment 1, and difference is not add auxiliary agent Ga and La, obtains catalyst DA,
Composition is shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst DA.
Catalyst reaction result under such state is denoted as DCat1, is specifically shown in Table 2 and table 3.
Comparative example 2
Specific implementation process is roughly the same with embodiment 1, and difference is not add auxiliary agent Ca and La, obtains catalyst DB,
Composition is shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst DB.
Catalyst reaction result under such state is denoted as DCat2, is specifically shown in Table 2 and table 3.
Comparative example 3
Specific implementation process is roughly the same with embodiment 1, and difference is not add auxiliary agent Ca and Ga, obtains catalyst DC,
Composition is shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst DC.
Catalyst reaction result under such state is denoted as DCat3, is specifically shown in Table 2 and table 3.
Comparative example 4
Specific implementation process is roughly the same with embodiment 1, and difference is not add any auxiliary agent, obtains catalyst DD, group
At being shown in Table 1.
This is connected using two reactor and carries out activity rating method with embodiment 1 to catalyst, and difference is second segment
Catalyst is catalyst DD.
Catalyst reaction result under such state is denoted as DCat4, is specifically shown in Table 2 and table 3.
Stability test
First segment catalyst is with embodiment 1, i.e., by Cu-ZnO-Al2O3Catalst for synthesis of methanol and γ-Al2O3Composition, is pressed
Mass ratio is the mixing of 1:1 particle, and second segment catalyst is 5%Ni-5%Cu-0.25%Ca-0.1%Ga-0.5%La/ β with embodiment 1
Molecular sieve catalyst, reaction carry out 100 hours.First segment initial reaction temperature is 275 DEG C, the constant guarantor of second segment reaction temperature
It holds at 350 DEG C, reaction pressure 4MPa, synthesis gas air speed 2500mL/h g.See Fig. 2.
The composition of each embodiment and comparative example catalyst of table 1
| Catalyst number | The content of Ni, wt% | The content of Cu, wt% | The content of Ca, wt% | The content of Ga, wt% | The content of La, wt% |
| A | 5.0 | 5.0 | 0.25 | 0.1 | 0.5 |
| B | 5.0 | 5.0 | 0.1 | 0.1 | 0.25 |
| C | 5.0 | 5.0 | 0.25 | 0.1 | 0.8 |
| D | 5.0 | 5.0 | 0.4 | 0.1 | 0.2 |
| E | 5.0 | 5.0 | 0.5 | 0.1 | 0.25 |
| F | 5.0 | 5.0 | 0.5 | 0.1 | 0.5 |
| G | 5.0 | 5.0 | 0.3 | 0.25 | 0.5 |
| H | 5.0 | 5.0 | 0.5 | 0.5 | 0.5 |
| I | 5.0 | 5.5 | 0.5 | 0.5 | 1.0 |
| J | 4.5 | 5.0 | 0.25 | 0.2 | 0.5 |
| DA | 5.0 | 5.0 | 0.25 | - | - |
| DB | 5.0 | 5.0 | - | 0.1 | - |
| DC | 5.0 | 5.0 | - | - | 0.5 |
| DD | 5.0 | 5.0 | - | - | - |
The evaluation result of each embodiment and comparative example catalyst of table 2
| XCO, % | S-CO2, % | S-LPG, wt% | Y-HC, % | |
| Cat1 | 81.03 | 10.26 | 78.52 | 72.72 |
| Cat2 | 80.48 | 11.05 | 78.26 | 71.59 |
| Cat3 | 79.18 | 11.33 | 77.57 | 70.21 |
| Cat4 | 79.15 | 11.52 | 77.25 | 70.03 |
| Cat5 | 79.34 | 11.39 | 77.59 | 70.30 |
| Cat6 | 79.10 | 11.76 | 77.43 | 69.80 |
| Cat7 | 80.05 | 11.26 | 77.26 | 71.04 |
| Cat8 | 79.57 | 12.16 | 77.62 | 69.89 |
| Cat9 | 79.40 | 12.04 | 77.11 | 69.84 |
| Cat10 | 79.25 | 12.01 | 77.31 | 69.73 |
| DCat1 | 77.56 | 19.49 | 75.97 | 62.44 |
| DCat2 | 77.13 | 19.91 | 75.79 | 61.92 |
| DCat3 | 77.48 | 19.56 | 75.43 | 62.32 |
| DCat4 | 77.06 | 21.98 | 75.86 | 60.12 |
Note: XCO- CO 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 and comparative example products therefrom of table 3
| C1 | C2 | C3 | C4 | C5 | C6 + | |
| Cat1 | 1.73 | 7.37 | 29.73 | 48.79 | 11.30 | 1.08 |
| Cat2 | 2.17 | 7.25 | 27.35 | 50.91 | 11.22 | 1.10 |
| Cat3 | 2.27 | 7.93 | 29.29 | 48.28 | 11.10 | 1.13 |
| Cat4 | 2.29 | 7.65 | 29.80 | 47.45 | 11.62 | 1.19 |
| Cat5 | 2.24 | 7.99 | 29.90 | 47.69 | 11.23 | 0.95 |
| Cat6 | 2.17 | 8.13 | 29.19 | 48.24 | 11.31 | 0.96 |
| Cat7 | 2.13 | 7.93 | 29.19 | 48.07 | 11.62 | 1.06 |
| Cat8 | 2.42 | 6.70 | 28.40 | 49.22 | 11.94 | 1.32 |
| Cat9 | 2.30 | 7.98 | 27.66 | 49.45 | 11.39 | 1.22 |
| Cat10 | 2.13 | 8.09 | 29.03 | 48.28 | 11.46 | 1.01 |
| DCat1 | 2.32 | 8.28 | 26.19 | 49.78 | 12.11 | 1.32 |
| DCat2 | 2.86 | 7.85 | 29.38 | 46.41 | 11.92 | 1.58 |
| DCat3 | 3.17 | 8.13 | 29.19 | 46.24 | 11.31 | 1.96 |
| DCat4 | 2.35 | 7.49 | 26.00 | 49.86 | 13.00 | 1.30 |
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| CN101773848A (en) * | 2010-01-14 | 2010-07-14 | 华东理工大学 | Catalyst used for synthesizing methyl tertiary butyl ether and preparation method thereof |
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| CN101745397B (en) * | 2008-12-18 | 2015-05-20 | 中国石油化工股份有限公司 | Method for preparing methanol, dimethyl ether and low-carbon olefin from synthesis gas |
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