CN102452878B - Method for preparing low-carbon olefin by synthetic gas one-step technology - Google Patents
Method for preparing low-carbon olefin by synthetic gas one-step technology Download PDFInfo
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- CN102452878B CN102452878B CN201010513651.2A CN201010513651A CN102452878B CN 102452878 B CN102452878 B CN 102452878B CN 201010513651 A CN201010513651 A CN 201010513651A CN 102452878 B CN102452878 B CN 102452878B
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Abstract
The invention relates to a method for preparing a low-carbon olefin by a synthetic gas one-step technology. The method aims at solving a problem that based on the prior art, a low-carbon olefin preparation process adopting a fixed bed Fischer-Tropsch synthesis technology has a low CO conversion rate and poor low-carbon olefin selectivity. The method solves the problem well by adopting a technical scheme of low-carbon olefin preparation adopting a fixed bed catalyst, wherein the technical scheme is characterized in that active alumina is utilized as a carrier; supported active ingredients contain compounds having an atomic ratio chemical formula of Fe100AaBbOx; A represents at least one of Cu and Mn; and B represents an alkali metal K. The method provided by the invention can be utilized for low-carbon olefin industrial production adopting synthetic gas.
Description
Technical field
The present invention relates to a kind of method for the synthesis of gas single stage method preparing low-carbon olefins.
Background technology
Low-carbon alkene refers to that carbonatoms is less than or equal to 4 alkene.The low-carbon alkene that ethene, propylene is representative of take is very important basic organic chemical industry raw material, and along with the rapid growth of China's economy, for a long time, supply falls short of demand in low-carbon alkene market.At present, the production of low-carbon alkene mainly adopts the petrochemical complex route of lighter hydrocarbons (ethane, petroleum naphtha, solar oil) cracking, day by day shortage and the long-term run at high level of crude oil price due to Global Oil resource, it is that the tube cracking furnace technique of raw material can run into an increasing raw material difficult problem that development low-carbon alkene industry only relies on oil lighter hydrocarbons, and low-carbon alkene production technique and raw material must diversification.Select synthetic gas to produce olefin process and can widen starting material sources, will take crude oil, Sweet natural gas, coal and recyclable materials as raw material production synthetic gas, for providing replacement scheme based on expensive raw material as the steam cracking technology aspect of petroleum naphtha.The direct preparing low-carbon olefins of one-step method from syngas is exactly that carbon monoxide and hydrogen are under catalyst action, by Fischer-Tropsch synthesis, directly make the process that carbonatoms is less than or equal to 4 low-carbon alkene, this technique without as indirect method technique from synthesis gas through methanol or dme, further prepare alkene, simplification of flowsheet, greatly reduces investment.
Synthetic gas synthesizes direct preparing low-carbon olefins by Fischer-Tropsch, has become one of study hotspot of fischer-tropsch synthetic catalyst exploitation.In the disclosed patent CN1083415A of Dalian Chemiclophysics Inst., Chinese Academy of Sciences, iron-Mn catalyst system that YongMgODeng IIA family's alkalimetal oxide or supersiliceous zeolite molecular sieve (or phosphorus aluminium zeolite) support, with highly basic K or Cs ion, make auxiliary agent, in preparation of low carbon olefines by synthetic gas reaction pressure, be 1.0～5.0MPa, at 300～400 ℃ of temperature of reaction, can obtain higher activity (CO transformation efficiency 90%) and selectivity (selectivity of light olefin 66%).In the patent ZL03109585.2 that Beijing University of Chemical Technology declares, adopt vacuum impregnation technology to prepare Fe/ activated-carbon catalyst that manganese, copper, zinc silicon, potassium etc. are auxiliary agent for the synthesis of gas reaction for preparing light olefins, under the condition without unstripped gas circulation, CO transformation efficiency 96%, the selectivity 68% of low-carbon alkene in hydrocarbon polymer.But CO transformation efficiency and the selectivity of light olefin of above-mentioned catalyzer in fixed bed reaction is all lower.
Summary of the invention
Technical problem to be solved by this invention is that in prior art, fixed bed Fischer-Tropsch synthesizes in preparing low carbon olefin hydrocarbon, CO transformation efficiency is lower, the lower problem of selectivity of light olefin in product, a kind of method of new one-step method from syngas preparing low-carbon olefins is provided, it is high that the method has CO transformation efficiency, the advantage that selectivity of light olefin is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of one-step method from syngas preparing low-carbon olefins, the synthetic gas that H2 and CO form of take is raw material, the mol ratio of H2 and CO is 1～3, in temperature of reaction, it is 300～400 ℃, reaction pressure is 1.0～3.0Mpa, and feed gas volume air speed is 500～1500h
-1condition under, unstripped gas contacts with fixed bed catalyst, generates the main alkene containing C2～C4, wherein catalyzer used be take activated alumina as carrier, load active component on carrier, active ingredient is with the following composition of atomic ratio measuring chemical formula:
Fe
100A
aB
bO
x
In formula, A is selected from least one in Cu, Mn;
B is selected from basic metal K;
The span of a is 20.0～70.0;
The span of b is 10.0～50.0;
X meets the required Sauerstoffatom sum of each element valence in catalyzer;
Carrier consumption is 30～80% of catalyst weight by weight percentage, and alumina catalyst support must be roasting 0.2～12 hour at 800～1200 ℃ in temperature before Kaolinite Preparation of Catalyst.
In technique scheme, the preparation method of the catalyzer using in the inventive method, comprises the following steps:
(1) active aluminum oxide carrier of the aequum of pickling is carried out to calcination process;
(2) by the molysite of aequum, mantoquita or manganese salt, and basic metal sylvite, the mixed solution I of making soluble in water;
(3), under vacuum condition, above-mentioned mixed solution I be impregnated on the alumina supporter of handling well in (1) step of aequum to obtain to catalyst precursor J;
(4), by catalyst precursor J, 400～800 ℃ of roastings are 0.5～5 hour after drying, obtain required catalyzer.
The calcination process temperature of described active aluminum oxide carrier is preferably 900～1100 ℃, and roasting time is preferably 1～4 hour.
The inventive method adopts vacuum impregnation technology Kaolinite Preparation of Catalyst, can make active ingredient and auxiliary agent height be dispersed in carrier surface, increases the quantity of the active sites that is exposed to carrier surface, improves the transformation efficiency of CO.
The inventive method adopts high-temperature roasting to process common active aluminum oxide carrier, can greatly reduce the surface acidity of carrier, avoids the after polymerization reaction of low-carbon alkene, improves the selectivity of low-carbon alkene; And obtain suitable pore structure, be conducive to shifting out fast of low-carbon alkene.
Using method of the present invention, is 1.5 in the mol ratio of H2 and CO, in temperature of reaction, is 350 ℃, and reaction pressure is 2.0Mpa, and feed gas volume air speed is 1000h
-1condition under, CO transformation efficiency can reach 98%, than prior art, improves 2%; The selectivity of low-carbon alkene in hydrocarbon polymer can reach 70%, than prior art, improves 2%.Obtained good technique effect.
Catalyzer prepared by the inventive method, molysite adopts iron nitrate, auxiliary agent mantoquita and manganese salt adopt respectively cupric nitrate and manganous nitrate, alkali metal promoter adopts saltpetre, be general reagent, carrier is conventional activated alumina shaping carrier, and preparation technology is simply easy, the preparation cost that has greatly reduced catalyzer, is applicable to large-scale industrial production.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The active aluminum oxide carrier of the aequum of pickling is carried out to calcination process roasting 1 hour at 1100 ℃ standby.By a certain amount of iron nitrate, manganous nitrate, the saltpetre mixed solution I that is made into certain proportion concentration soluble in water.Under vacuum condition, above-mentioned mixed solution I be impregnated on the alumina supporter of handling well of aequum to obtain to catalyst precursor J.The catalyst precursor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 600 ℃ of maturing temperatures, and roasting time 2h, obtains the catalyzer for the synthesis of gas single stage method preparing low-carbon olefins, and it is made and consists of:
35％Fe
100Mn
50K
30O
x+65％Al
2O
3。
Prepared catalyzer carries out the experimental result of one-step method from syngas preparing low-carbon olefins and lists in table 1 under certain reaction conditions.
[embodiment 2]
The active aluminum oxide carrier of the aequum of pickling is carried out to calcination process roasting 2 hours at 900 ℃ standby.By a certain amount of iron nitrate, manganous nitrate, the saltpetre mixed solution I that is made into certain proportion concentration soluble in water.Under vacuum condition, above-mentioned mixed solution I be impregnated on the alumina supporter of handling well of aequum to obtain to catalyst precursor J.The catalyst precursor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 600 ℃ of maturing temperatures, and roasting time 2h, obtains the catalyzer for the synthesis of gas single stage method preparing low-carbon olefins, and it is made and consists of:
35％Fe
100Mn
50K
30O
x+65％Al
2O
3。
Prepared catalyzer carries out the experimental result of one-step method from syngas preparing low-carbon olefins and lists in table 1 under certain reaction conditions.
[embodiment 3]
The active aluminum oxide carrier of the aequum of pickling is carried out to calcination process roasting 1 hour at 1100 ℃ standby.By a certain amount of iron nitrate, manganous nitrate, the saltpetre mixed solution I that is made into certain proportion concentration soluble in water.Under vacuum condition, above-mentioned mixed solution I be impregnated on the alumina supporter of handling well of aequum to obtain to catalyst precursor J.The catalyst precursor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 400 ℃ of maturing temperatures, and roasting time 8h, obtains the catalyzer for the synthesis of gas single stage method preparing low-carbon olefins, and it is made and consists of:
35％Fe
100Mn
50K
30O
x+65％Al
2O
3。
Prepared catalyzer carries out the experimental result of one-step method from syngas preparing low-carbon olefins and lists in table 1.
[embodiment 4]
The active aluminum oxide carrier of the aequum of pickling is carried out to calcination process roasting 1 hour at 1100 ℃ standby.By a certain amount of iron nitrate, manganous nitrate, the saltpetre mixed solution I that is made into certain proportion concentration soluble in water.Under vacuum condition, above-mentioned mixed solution I be impregnated on the alumina supporter of handling well of aequum to obtain to catalyst precursor J.The catalyst precursor J having flooded is dry under 110 ℃ of conditions, then carries out roasting, 800 ℃ of maturing temperatures, and roasting time 0.5h, obtains the catalyzer for the synthesis of gas single stage method preparing low-carbon olefins, and it is made and consists of:
35％Fe
100Mn
50K
30O
x+65％Al
2O
3。
Prepared catalyzer carries out the experimental result of one-step method from syngas preparing low-carbon olefins and lists in table 1 under certain reaction conditions.
[embodiment 5～8]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyzer that form, gained catalyzer numbering and composition are respectively:
Embodiment 5 50%Fe
100mn
75k
28o
x+ 50%Al
2o
3
Embodiment 6 25%Fe
100cu
20k
50o
x+ 75%Al
2o
3.
Embodiment 7 45%Fe
100cu
40k
20o
x+ 55%Al
2o
3
Embodiment 8 35%Fe
100mn
50cu
40k
30o
x+ 65%Al
2o
3
Prepared catalyzer carries out the experimental result of one-step method from syngas preparing low-carbon olefins and lists in table 1 under certain reaction conditions.
[comparative example 1～3]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyzer that form, gained catalyzer numbering and composition are respectively:
Comparative example 1 35%Fe
100mn
50o
x+ 65%Al
2o
3
Comparative example 2 25%Fe
100cu
50o
x+ 75%Al
2o
3
Comparative example 3 35%Fe
100mn
50k
30ox+65%C
Prepared catalyzer carries out the experimental result of one-step method from syngas preparing low-carbon olefins and lists in table 1 under certain reaction conditions.
[comparative example 4]
Adopt method Kaolinite Preparation of Catalyst substantially the same manner as Example 1, just the active aluminum oxide carrier of the aequum of pickling does not carry out calcination process, and gained catalyzer numbering and composition are respectively:
Comparative example 4 35%Fe
100mn
50k
30o
x+ 65%Al
2o
3.
Prepared catalyzer carries out the experimental result of one-step method from syngas preparing low-carbon olefins and lists in table 1 under certain reaction conditions.
The reductive condition of above-described embodiment and comparative example is:
450 ℃ of temperature
Pressure normal pressure
Loaded catalyst 3ml
Catalyst loading 1000 hours
-1
Reducing gas H
2
8 hours recovery times
Reaction conditions is:
350 ℃ of temperature of reaction
Reaction pressure 2.0MPa
Loaded catalyst 3ml
Catalyst loading 1000 hours
-1
Proportioning raw materials (mole) H
2/ CO=2.0/1
The evaluation result of table 1 embodiment catalyzer
[embodiment 8]
Each step and the condition Preparation and evaluation catalyzer of pressing embodiment 2, just change appreciation condition, and its appraisal result is listed in table 2.
The evaluation result of catalyzer under table 2 different evaluation condition
Claims (1)
1. a method for one-step method from syngas preparing low-carbon olefins, carries out calcination process roasting 1 hour at 1100 ℃ by the active aluminum oxide carrier of the aequum of pickling standby; By a certain amount of iron nitrate, manganous nitrate, the saltpetre mixing solutions that is made into certain proportion concentration soluble in water; Under vacuum condition, above-mentioned mixing solutions be impregnated on the alumina supporter of handling well of aequum to obtain to catalyst precursor; The catalyst precursor having flooded is dry under 110 ℃ of conditions, then carries out roasting, 600 ℃ of maturing temperatures, and roasting time 2h, obtains the catalyzer for the synthesis of gas single stage method preparing low-carbon olefins, and it is made and consists of: 35%Fe
100mn
50k
30o
x+ 65%Al
2o
3;
Prepared catalyzer is carrying out one-step method from syngas preparing low-carbon olefins under certain reaction conditions, and evaluation result shows that its CO transformation efficiency is that the selectivity of 98.1%, C2～C4 alkene is 70.6wt%;
The reductive condition of above-mentioned catalyzer is:
450 ℃ of temperature
Pressure normal pressure
Loaded catalyst 3ml
Catalyst loading 1000 hours
-1
Reducing gas H
2
8 hours recovery times
Reaction conditions is:
millimeter fixed-bed reactor
350 ℃ of temperature of reaction
Reaction pressure 2.0MPa
Loaded catalyst 3ml
Catalyst loading 1000 hours
-1
Proportioning raw materials (mole) H
2/ CO=2.0/1.
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| CN114425362B (en) * | 2020-10-14 | 2023-10-31 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin, preparation method and application thereof |
| CN115155588A (en) * | 2022-08-25 | 2022-10-11 | 南京工业大学 | Series catalyst for preparing aromatic hydrocarbon by direct hydrogenation of carbon dioxide and preparation method and application thereof |
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