CN101658805B - Method for preparing catalyst for synthesizing LPG by synthetic gas in one-step method - Google Patents
Method for preparing catalyst for synthesizing LPG by synthetic gas in one-step method Download PDFInfo
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- CN101658805B CN101658805B CN2009101923959A CN200910192395A CN101658805B CN 101658805 B CN101658805 B CN 101658805B CN 2009101923959 A CN2009101923959 A CN 2009101923959A CN 200910192395 A CN200910192395 A CN 200910192395A CN 101658805 B CN101658805 B CN 101658805B
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- lpg
- solid acid
- acid catalyst
- catalyst
- molecular sieve
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Abstract
The invention discloses a method for preparing a catalyst for preparing LPG by synthetic gas in a one-step method. The method comprises the following steps: taking Cu(NO3)2, Zn(NO3)2 and Al(NO3)3 according to the mole ratio of 6+/-0.6:3+/-0.3:1+/-0.1 as raw materials, drying after carrying out coprecipitation with oxalic acid, calcining, obtaining a copper base catalyst, then mixing with a solid acid catalyst according to the weight ratio of 1-5:1 and tabletting; or, after modifying the solid acid catalyst, mixing the copper base catalyst and the modified solid acid catalyst according to the weight ratio of 1-5:1 and tabletting. The method for preparing the LPG catalyst is simple, and the LPG obtained by preparation has large selectivity of a target product and longer service life of the catalyst; the requirement of synthesizing the LPG by synthetic gas with high hydrogen-carbon ratio and synthetic gas with low hydrogen-carbon ratio in one step can be met.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, relate in particular to a kind of Preparation of catalysts method that is used for the synthetic liquefied petroleum gas (LPG) of one-step method from syngas.
Technical background
LPG refers to pressurization (about about 1 MPa) under the normal temperature and the oil gas of liquefaction.Its main component is that propane, propylene, normal butane, iso-butane, fourth are rare-1, maleic-2, anti-butene-2 and isobutene etc., is commonly called as carbon three (C
3) and carbon four (C
4), and a spot of methane, ethane, pentane, ethene and amylene, be commonly called as carbon one (C
1), carbon two (C
2) and carbon five (C
5).The quality of LPG is relevant with its source and extracting method, and the quality of the LPG that generally obtains from associated gas is better than the liquefied petroleum gas that obtains from oil plant oil gas.Simultaneously, by the LPG physicochemical properties in the table 1 as can be known, LPG can store transportation in liquid mode easily.
The basic physicochemical properties of table 1LPG
Along with the exhaustion of fossil energy, the human severe challenge that faces limited resources in coming few decades at last.China is the poor relatively country of petroleum resources, and rising steadily of international oil price produced material impact to China's economy in recent years, and the energy security and the national security of China are also brought sizable pressure simultaneously.Living beings are unique carbon resources that are converted into liquid fuel in the regenerative resource, biogas by developing low-cost is combined to liquid fuel technology, with synthetic high-quality alternative energy source and the chemicals of the living resources of discarded object, the application technology of LPG is very ripe simultaneously, utilize the method for living beings renewable resource by heat chemistry conversion, catalyzed conversion, prepare reproducible LPG, for realizing that China's energy resource structure diversification, enhancing energy security have great importance.
U.S. Patent No. 10/929,841 and Japan Patent No.2004-200333 disclose a kind of technology of synthetic LPG catalyst, and it is that platinum base catalyst for methanol and beta molecular sieve fully mix made.Utilizing this catalyst to synthesize in the LPG process, catalyst has the advantage of high activity, high selectivity and high yield, but is not suitable for the low hydrogen-carbon ratio synthesis gas, and catalyst life is shorter simultaneously.
Existing synthetic LPG catalyst is applicable to that mainly synthesis gas is at H
2/ CO 〉=2 o'clock, along with the maturation of biomass gasification technology, for the low hydrogen-carbon ratio of living beings oxygen enrichment, oxygen enrichment-steam gasification gained at H
2/ CO＜2 o'clock are badly in need of that a kind of suitable scope is wideer, the better synthetic LPG catalyst of stability.
Summary of the invention
The objective of the invention is at low hydrogen-carbon ratio in the prior art at H
2/ CO＜2 do not have suitable LPG catalyst, and a kind of accommodation is wider, stability is used for the Preparation of catalysts method that synthesis gas is directly made LPG better and provide.
For achieving the above object, the present invention has taked following technical scheme:
A kind ofly be used for the Preparation of catalysts method that one-step method from syngas prepares LPG, may further comprise the steps:
(1) with Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
3Be dissolved in absolute ethyl alcohol be made into nitrate mixed solution at 6 ± 0.6: 3 ± 0.3: 1 ± 0.1 in molar ratio; Oxalic acid is dissolved in absolute ethyl alcohol is made into oxalic acid solution; The mol ratio of described nitrate mixed solution and oxalic acid solution is 1: 1;
(2) nitrate mixed solution and oxalic acid solution and stream are titrated in a small amount of absolute ethyl alcohol of vigorous stirring;
(3) leave standstill 1-3 hour, suction filtration, 65-85 ℃ of drying, the roasting cooling obtains copper-based catalysts;
(4) step (3) gained copper-based catalysts and solid acid catalyst are crushed to respectively below 100 orders, by weight 1-5: 1 mixed pressuring plate.
The roasting condition of described step (3) is: following 8 hours of 110 ℃ of conditions, by 110 ℃ of temperature programmings to 335 ℃, constant temperature calcining is 4 hours again.
Described solid acid catalyst is HZSM-5 type molecular sieve, beta molecular sieve, HY type molecular sieve, γ-Al
2O
3In one or more.
Preferably, described preparation method also comprises solid acid catalyst is carried out modification, may further comprise the steps:
(1) with solid acid catalyst 500-600 ℃ roasting 1-3 hour, naturally the cooling;
(2) with Mg (NO
3)
2.6H
2After the O crystal is dissolved in absolute ethyl alcohol, add the solid acid catalyst through step (1) roasting cooling, incipient impregnation under the vigorous stirring makes MgO account for the ratio that the solid acid catalyst weight ratio is 0.01-2%;
(3) 65-85 ℃ of drying, the roasting cooling obtains modified solid acid catalyst.
Preferably, the weight ratio of described copper-based catalysts and modified solid acid catalyst is 2: 1, under this ratio condition, and the conversion ratio height of CO, C
3+ C
4The space-time yield height.
Preferably, it is 0.25-2% that described MgO accounts for solid acid catalyst weight, under this ratio condition, and the conversion ratio height of CO, C
3+ C
4The space-time yield height.
Described drying condition is preferably 80 ℃ of drying with water baths, and drying with water bath has more stable heating-up temperature, helps modified solid acid catalyst and forms crystal, has the good homogeneous degree.
Roasting condition is in the described step (3): constant temperature is 2 hours under 110 ℃ of conditions, temperature programming to 335 ℃, and constant temperature 4h, temperature programming to 460 ℃ constant temperature is 4 hours then.
LPG Preparation of catalysts method of the present invention is simple, and the LPG catalyst grain size for preparing is little, and the specific area height has higher activity, and target product selectivity is big, has long catalyst service life; LPG catalyst of the present invention is applied widely simultaneously, can satisfy the needs of high hydrogen-carbon ratio synthesis gas and synthetic LPG of one step of low hydrogen-carbon ratio synthesis gas.
The specific embodiment
Below in conjunction with embodiment the present invention is described.Below each embodiment can further specify the present invention, but do not limit its practical range.Be that example describes with copper-based catalysts (mol ratio Cu: Zn: Al=6: 3: 1) and HZSM-5 type modified molecular screen as modified solid acid catalyst among the embodiment, used solid acid catalyst can be any solid acid catalyst, be preferably HZSM-5 type molecular sieve, beta molecular sieve, HY type molecular sieve, γ-Al
2O
3Wherein one or more, below also to have used modenite be that example illustrates.
Embodiment 1:Cat1 (copper-based catalysts: modified HZSM-5 type molecular sieve=2: 1, MgO content are 2wt%)
(1) with total concentration is the Cu (NO of 1.0mol/L
3)
2, Zn (NO
3)
2And Al (NO
3)
3(wherein mol ratio Cu: Zn: Al=6: 3: 1) is dissolved in absolute ethyl alcohol and is placed in the separatory funnel, and the oxalic acid solution of getting 1.0mol/L is dissolved in absolute ethyl alcohol and is placed in another separatory funnel;
(2) both and stream are titrated in the absolute ethyl alcohol that a small amount of high-speed stirred, and form flocculent deposit;
(3) after precipitation was finished, suction filtration after static 2 hours carried out drying under 80 ℃ of water bath condition, move to roasting in the Muffle furnace, under 110 ℃ of conditions the oven dry 8 hours, then 2 hours by 110 ℃ of temperature programmings (5 ℃/min) to 335 ℃, roasting 4 hours, cooling makes copper-based catalysts naturally, is crushed to 100 orders.
(4) 10g HZSM-5 type molecular sieve (commercialization) is cooled off after two hours through 550 ℃ of roastings, be crushed to 100 orders.
(5) with 1.28g Mg (NO
3)
2.6H
2The O crystal is dissolved in the 50ml absolute ethyl alcohol, after the dissolving fully, adds the HZSM-5 type molecular sieve of step (4), incipient impregnation under the vigorous stirring.
Unnecessary absolute ethyl alcohol is reclaimed in evaporation under (6) 80 ℃ of water bath condition, the gained sediment moves into roasting in the Muffle furnace, constant temperature is 2 hours under 110 ℃ of conditions, temperature programming (5 ℃/min) to 335 ℃, constant temperature 4h, temperature programming then (5 ℃/min) to 460 ℃ of constant temperature 4 hours, cooling naturally, obtain containing the modified HZSM-5 type molecular sieve of MgO 2% (mass content), be crushed to 100 orders.
(7) get 2g 100 order copper-based catalysts and 1g 100 order MgO modified HZSM-5 type molecular sieves, physical mixed is the back compressing tablet evenly, and it is standby to get the 20-40 order.Be designated as Cat1.
Embodiment 2:Cat2 (copper-based catalysts: modified HZSM-5 type molecular sieve=2: 1, MgO content are 1wt%) method and condition just when the commercial HZSM-5 type of modification molecular sieve, add Mg (NO with embodiment 1
3)
2.6H
2The amount of O makes 0.64g into, contains MgO 1% (mass content) in the modified HZSM-5 type molecular sieve of gained.Be designated as Cat2.
Embodiment 3:Cat3 (copper-based catalysts: modified HZSM-5 type molecular sieve=2: 1, MgO content are 0.5wt%)
Method and condition just when the commercial HZSM-5 type of modification molecular sieve, add Mg (NO with embodiment 1
3)
2.6H
2The amount of O makes 0.32g into, contains MgO 0.5% (mass content) in the modified HZSM-5 type molecular sieve of gained.Be designated as Cat3.
Embodiment 4:Cat4 (copper-based catalysts: modified HZSM-5 type molecular sieve=2: 1, MgO content are 0.25wt%)
Method and condition just when the commercial HZSM-5 type of modification molecular sieve, add Mg (NO with embodiment 1
3)
2.6H
2The amount of O makes 0.16g into, contains MgO0.25% (mass content) in the modified HZSM-5 type molecular sieve of gained.Be designated as Cat4.
Embodiment 5:Cat5 (copper-based catalysts: HZSM-5 type molecular sieve=2: 1, MgO content are 0)
Method and condition directly with copper-based catalysts for preparing and commercial HZSM-5 type molecular sieve mixed pressuring plate, do not contain MgO with embodiment 1.Be designated as Cat5.
Below the synthetic catalyst of embodiment 1-5 is estimated, synthesis gas is with H
2/ CO=1.5 is that example describes, and this catalyst is used in synthesis gas H
2/ CO＞0.8 o'clock any synthesis gas.
The term that uses among the present invention " synthesis gas " is meant the mist that contains hydrogen and carbon monoxide, and it is not limited to the mist be made up of hydrogen and carbon monoxide.Such synthesis gas can be, for example, and the mist of carbonated, water vapour, methane, ethane, ethene etc.
On miniature fixed bed continuous-flow reaction unit, carry out the catalyst activity evaluation.The 2mL catalyst is loaded on the flat-temperature zone of reaction tube, uses VH
2: VN
2=5: 95 mist is by certain heating schedule, and through 110 ℃, 140 ℃, 160 ℃, 220 ℃ and 270 ℃ are reduced by room temperature, and the reducing gases air speed is 1000h
-1, whole reduction process continues about 9h.After the catalyst reduction, reducing gases is switched to synthesis gas.Consisting of of synthesis gas: VH
2: VCO: VCO
2: VN
2: VCH
4=53: 35: 4: 3: 5.Make pressure rise to reaction pressure 2.1MPa, air speed is 2000h
-1Rise to 325 ℃ of optimal reaction temperatures since 270 ℃ of heating rates then with 5 ℃/min.
From table 2-table 4 as can be seen, obviously be better than with copper-based catalysts and the synthetic LPG catalyst (MgO content is 0) of solid acid catalyst with copper-based catalysts and synthetic LPG catalyst (MgO content the is 0.25-2wt%) effect of modified solid acid catalyst.By the CO conversion ratio height of the synthetic catalyst of copper-based catalysts and modified solid acid catalyst, C
3+ C
4The space-time yield height.Best results when MgO content is 0.5wt%.
Table 2 is reflected at 325 ℃, 2.1MPa, air speed=2000h
-1, result during reaction 20h
325 ℃ in table 3,2.1MPa, 2000h
-1Each catalyst under the condition is with reaction time CO conversion ratio
325 ℃ in table 4,2.1MPa, 2000h
-1Each catalyst under the condition is with reaction time C3+C4 space-time yield
Embodiment 6:Cat6 (copper-based catalysts: modified HZSM-5 type molecular sieve=5: 1, MgO content are 0.5wt%)
Method and condition are copper-based catalysts: modified HZSM-5 type molecular sieve=5: 1 with embodiment 1.Be designated as Cat6.
Embodiment 7:Cat7 (copper-based catalysts: modified HZSM-5 type molecular sieve=1: 1, MgO content are 0.01wt%)
Method and condition are copper-based catalysts: modified HZSM-5 type molecular sieve=1: 1 with embodiment 1.Be designated as Cat7.
Embodiment 8:Cat8 (copper-based catalysts: modification HY type molecular sieve=1: 1, MgO content is 2wt%)
Method and condition are with embodiment 1, and just the solid catalyst of usefulness is a HY type molecular sieve, copper-based catalysts: modification HY type molecular sieve=1: 1.Be designated as Cat8.
Embodiment 9:Cat9 (copper-based catalysts: modification HY type molecular sieve=2: 1, MgO content is 0.01wt%)
Method and condition are with embodiment 1, and just the solid catalyst of usefulness is a HY type molecular sieve, copper-based catalysts: modification HY type molecular sieve=2: 1.Be designated as Cat9.
Embodiment 10:Cat10 (copper-based catalysts: modification HY type molecular sieve+γ-Al
2O
3=2: 1, MgO content is 1wt%)
Method and condition are with embodiment 1, and just the solid catalyst of usefulness is HY type molecular sieve+γ-Al
2O
3, copper-based catalysts: modification HY type molecular sieve+γ-Al
2O
3=2: 1.Be designated as Cat10.
Embodiment 11:Cat11 (copper-based catalysts: HZSM-5 type molecular sieve+HY type molecular sieve+γ-Al
2O
3=2: 1, MgO content is 0.1wt%)
Method and condition are with embodiment 1, and just the solid catalyst of usefulness is HZSM-5 type molecular sieve+HY type molecular sieve+γ-Al
2O
3, copper-based catalysts: modified HZSM-5 type molecular sieve+HY type molecular sieve+γ-Al
2O
3=2: 1.Be designated as Cat11.
Embodiment 12:Cat12 (copper-based catalysts: modified mordenite=5: 1, MgO content are 0.5wt%)
Method and condition are copper-based catalysts: modified mordenite=5: 1 with embodiment 1.Be designated as Cat12.
Claims (7)
1. one kind is used for the Preparation of catalysts method that one-step method from syngas prepares LPG, it is characterized in that: may further comprise the steps:
(1) with Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
3Be dissolved in absolute ethyl alcohol be made into nitrate mixed solution at 6 ± 0.6: 3 ± 0.3: 1 ± 0.1 in molar ratio; Oxalic acid is dissolved in absolute ethyl alcohol is made into oxalic acid solution; The molar concentration rate of described nitrate mixed solution and oxalic acid solution is 1: 1;
(2) nitrate mixed solution and oxalic acid solution and stream are titrated in a small amount of absolute ethyl alcohol of vigorous stirring;
(3) leave standstill 1-3 hour, suction filtration, 65-85 ℃ of drying, the roasting cooling obtains copper-based catalysts;
(4) step (3) gained copper-based catalysts and modified solid acid catalyst are crushed to respectively below 100 orders, by weight 1-5: 1 mixed pressuring plate, described modified solid acid catalyst is prepared by following steps and gets:
(a) with solid acid catalyst 500-600 ℃ roasting 1-3 hour, naturally the cooling;
(b) with Mg (NO
3)
2.6H
2After the O crystal is dissolved in absolute ethyl alcohol, add solid acid catalyst through step (a) roasting cooling, incipient impregnation under the vigorous stirring, making MgO account for the solid acid catalyst weight ratio is 0.01-2%;
(c) 65-85 ℃ of drying, the roasting cooling obtains modified solid acid catalyst.
2. according to claim 1ly be used for the Preparation of catalysts method that one-step method from syngas prepares LPG, it is characterized in that: roasting condition is in the described step (3): following 8 hours of 110 ℃ of conditions, by 110 ℃ of temperature programmings to 335 ℃, constant temperature calcining is 4 hours again.
3. according to claim 1ly be used for the Preparation of catalysts method that one-step method from syngas prepares LPG, it is characterized in that: described solid acid catalyst is HZSM-5 type molecular sieve, beta molecular sieve, HY type molecular sieve, γ-Al
2O
3In one or more.
4. according to claim 1ly be used for the Preparation of catalysts method that one-step method from syngas prepares LPG, it is characterized in that: the weight ratio of described copper-based catalysts and modified solid acid catalyst is 2: 1.
5. according to claim 1ly be used for the Preparation of catalysts method that one-step method from syngas prepares LPG, it is characterized in that: it is 0.25-2% that described MgO accounts for modified solid acid catalyst weight.
6. according to claim 1ly be used for the Preparation of catalysts method that one-step method from syngas prepares LPG, it is characterized in that: drying condition is 80 ℃ of drying with water baths in the described step (c).
7. according to claim 1ly be used for the Preparation of catalysts method that one-step method from syngas prepares LPG, it is characterized in that: roasting condition is in the described step (c): constant temperature is 2 hours under 110 ℃ of conditions, temperature programming to 335 ℃, constant temperature 4h, temperature programming to 460 ℃ constant temperature is 4 hours then.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413767A (en) * | 2001-10-26 | 2003-04-30 | 中国科学院大连化学物理研究所 | Preparation method of catalyst for directed preparing dimethyl ether by synthetic gas |
| CN1785519A (en) * | 2004-12-08 | 2006-06-14 | 中国科学院广州能源研究所 | Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method |
-
2009
- 2009-09-16 CN CN2009101923959A patent/CN101658805B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413767A (en) * | 2001-10-26 | 2003-04-30 | 中国科学院大连化学物理研究所 | Preparation method of catalyst for directed preparing dimethyl ether by synthetic gas |
| CN1785519A (en) * | 2004-12-08 | 2006-06-14 | 中国科学院广州能源研究所 | Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method |
Non-Patent Citations (1)
| Title |
|---|
| 吕永兴等.HZSM-5对生物质合成气一步法合成LPG的影响.《现代化工》.2008,第28卷(第S2期),69，70. * |
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