CN1059318A - A kind of catalysis process by hydrocarbon conversion and combustion reactions production of synthetic gas in next life - Google Patents

A kind of catalysis process by hydrocarbon conversion and combustion reactions production of synthetic gas in next life Download PDF

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CN1059318A
CN1059318A CN91108515A CN91108515A CN1059318A CN 1059318 A CN1059318 A CN 1059318A CN 91108515 A CN91108515 A CN 91108515A CN 91108515 A CN91108515 A CN 91108515A CN 1059318 A CN1059318 A CN 1059318A
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reaction
combustion reactions
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hydrocarbon
conversion reaction
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卢卡·巴丝尼
玛里奥·马齐昂纳
多梅尼克·桑福里普
斯蒂芬·罗丝尼
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Snamprogetti Joint Stock Co Ltd
SnamProgetti SpA
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Abstract

The invention describes a kind of catalysis process from the hydrocarbon production synthetic gas, it is characterized in that it carries out two-step reaction in one or more reactors, the first step is carried out the combustion reactions of heat release, hydrocarbon or hydrocarbon mixture or carbon and air and/or oxygen are reacted, second step was carried out conversion reaction, and catalyst system contains:
---one or more platinum group metal compounds;
---a kind of carrier of being made up of mineral compound, in catalyst system, the weight percent of platinum metals is between 0.01-20%.

Description

A kind of catalysis process by hydrocarbon conversion and combustion reactions production of synthetic gas in next life
The present invention relates to a kind of catalysis process that adopts hydrocarbon conversion and combustion reactions production of synthetic gas in next life.
Synthetic gas is a kind of gaseous mixture, and this mixture mainly contains carbon monoxide and hydrogen, but also may contain more a spot of CH 4, CO 2And N 2Synthetic gas is as the reactant of large-scale chemical process, as the production of production, Fischer-Tropsch process and the ammonia of methyl alcohol.The most generally the synthetic gas production method of Cai Yonging comprises: the steam reforming of hydrocarbon, from thermal transition and non-catalytic partial oxidation.
Steam reforming (is typically Sweet natural gas and steam mixture is catalytically converted into H with hydro carbons 2/ CO is than the CO and the H that are about 3 2Mixture.The principal reaction that relates to is as follows:
Present method catalyzer commonly used is to be stated from Al, Mg with high thermal stability and the Ni on the Si oxide compound.
Temperature in two conversion systems all surpasses 850 ℃, and pressure is between 10-45MPa.
(referring to as " Catalysis-Science and Technology "-Vol.5, (1984), 1-J.R.Rostrup-Nielsen).
The method of partial oxidation is of little use, and it is used for the mixture of heavy hydrocarbon and oxygen is changed into synthetic gas.The principles of chemistry of present method can be described with following formula:
The factory that is built at present (by Texaco and Shell company built-referring to Hydrocarbon Processing-April(1990), 99) non-catalytic partial oxidation that relates under 1250 ℃-1500 ℃ and 3-12MPa reacts.
The self-heating conversion method is the integrated process of the steam reforming reaction of the part chlorination reaction of heat release and heat absorption.In present method, produce H as charging with hydrocarbon, steam and oxygen 2With the CO mixture.Its H 2/ CO is than between steam reforming and partial oxidation process.From thermal transition is a kind of catalysis process, and the catalyzer that this method is used is identical with steam reforming.
The temperature of reaction of using is between 800 ℃-1000 ℃, and pressure is between the 2.0-4.0MPa.
Be surprised to find that a kind of method now.This method makes and can produce synthetic gas under than the low temperature of at present used method by utilizing incendiary product and heat.
Present method is characterized in that carrying out two-step reaction with the hydrocarbon production synthetic gas in one or more reactors.In the first step, carry out the heat release combustion reactions, the mixture of a kind of hydrocarbon or hydrocarbon or carbon and air and/or oxygen are reacted, available following principal reaction is described usually:
In second step, the heat that utilizes combustion reactions to produce carries out conversion reaction, make combustion reaction products and carbonatoms be no more than 10 hydrocarbon or hydrocarbon mixture basically and react under a kind of effect of catalyst system, the main thermo-negative reaction below available is usually described:
This catalyst system comprises:
The compound of-one or more platinum metals, preferably selected from rhodium, ruthenium, palladium and platinum;
-a kind of carrier of being made up of mineral compound, wherein, the weight percent of catalyst system platinum metals is preferably between the 0.1-3% between 0.01-20%.
These two reactions steps need not the existing of steam (except that the steam that the combustion reactions of first reactions steps produces), thus steam whether to add be arbitrarily.
Carrier preferably is made up of the oxide compound that is selected from aluminium, magnesium, zirconium, silicon, cerium and/or lanthanum and/or its spinel one class mineral compound.This mineral compound exists with itself form or mutual bonded form.If necessary, also can there be basic metal to exist.
Used carrier can be made up of the silicide oxide of aluminium, magnesium, cerium or lanthanum.
The specific surface preferable range of used catalyst system is at 1-400m 2Between/the g, particularly at 10-200m 2Between/the g, and pore volume is preferably between 0.1-3ml/g, particularly between 0.5-2ml/g.
This catalyst system can make like this: the solution impregnation mineral compound with platinum group metal salts, then carry out heat drying and calcination process; Perhaps mineral compound is dispersed in a kind of organic solvent, in carbon monoxide or inert atmosphere, makes it then to react with platinum group metal compounds solution.
Normally heat release of second method after reaction, can produce band look material.Filter, drying and calcination process.
Or rather, described catalyst system makes like this: under 0 ℃-150 ℃, be preferably under 20 ℃-50 ℃, make the organometallics that is dissolved in the platinum metals in the organic solvent and the above-mentioned mineral compound that is dispersed in the described solvent carry out heterogeneous solid-liquid reaction.
After this step, mainly determine by the chemical property of inorganic oxide attached to the amount of metal on the matrix, rather than determine by its porosity and specific surface.
And the latter is important to the integrity of catalyzer in the conversion reaction process and stability.
The method that preparation contains aluminium, magnesium, cerium or lanthanum silicide oxide carrier mainly comprises between the silicon compound that makes aluminium, magnesium, caesium or lanthanum inorganic oxide and contain hydrolyzable organic group carries out condensation reaction, then, remove unhydrolysed organic residue by combustion reactions or under the condition that steam exists.
By these silicide step, just can obtain siliceous weight percent and be 0.5-15%, the material of 1-10% preferably.
The system that above-mentioned catalyst system can make reaction formula (2) and (3) describe in 300-1200 ℃ of this wide temperature range, obtains the transformation efficiency near the thermodynamic(al)equilibrium transformation efficiency.
This catalyst system also can adopt high H 2O/C is than the reactant of (by the mole number of the mole number/carbon of water vapor in the reactant).If necessary, even when not having water vapor in the reaction mixture, also can be from lighter hydrocarbons and CO 2Obtain synthetic gas.It is to be noted the H of the reaction mixture in second step especially 2The O/C ratio can reduce to 0.01, yet preferably selects 0.5-4.At present, in traditional steam reformer, when the reactant that uses is Sweet natural gas, H 2The O/C ratio is 2.5-3, when the reactant that uses is liquefied petroleum gas (LPG) or petroleum naphtha, and H 2O/C is than being 3-5.
The H of reaction mixture 2O/C is than influencing:
A) formation reaction of carbon
B) H of product mixture 2/ CO ratio
C) balance of water-gas shift reaction
D) conversion process technology.
In the production process of synthetic gas, may adopt low H 2O/C according to reaction formula (2) and (3), when only using a catalytic conversion reactor, can obtain the mixture of high CO content than reaction mixture.Moreover, when catalysis process is intended to produce hydrogen, behind conversion reactor, connect-be used for the water-gas shift catalyticreactor, use low H 2O/C is than reactant, and hydrogen output that can the unit's of making hydrocarbon consumption increases.
Two reactions steps of the employing that the present invention describes are produced the catalysis process of synthetic gas, also can make all CO that produce in the first step combustion reactions (1) 2And heat, in conversion reaction (2) and (3), utilized, thereby significantly reduced environmental pollution.
At present, in steam reformer, being necessary increases a reactor (twice transformation) in first tubular reactor (once transforming) back.First reactor is in about 800 ℃ of operations down, and steam and hydrocarbon mixture are as raw material, and second reactor is in about 1000 ℃ of operations down.The purpose of this structure is to obtain high reaction-ure conversion-age, makes the H of the product mixtures of second step of converting outlet 2/ CO ratio is less than 3.
Whether adopt catalyzed reaction as for combustion reactions, depend on the composition of used reactant.If combustion reactions is a catalyzed reaction, all known burnings all can be used with catalyzer, come the characteristic of selecting catalyst according to the composition of reaction mixture.
Known combustioncatalysts can be divided into two classes: metal catalyst and oxide catalyst.
Typical metal burning catalyzer is silicon-dioxide and carrying alumina Pt, Pd, Rh, Cu or Ag.
The oxide compound of IV family element can be used as the oxide compound combustioncatalysts, as TiO 2, V 2O 3, Cr 2O 3, MnO 2, Fe 2O 3, Co 3O 4, NiO, CuO, ZnO.
Under the ambident situation, combustioncatalysts can be the catalyst system that is similar to as transforming, that is, they can contain same platinum metals.
If combustion reactions is uncatalyzed reaction, a burner is arranged at the autothermic reactor inlet.
Only use a reactor, not only carry out combustion reactions but also can carry out conversion reaction, if combustion reactions is a catalyzed reaction, the beds of conversion reaction may be that separate or adjacent with the beds of combustion reactions; If all be uncatalyzed reaction, one burner arranged in the ingress of autothermic reactor.
The method according to this invention can obtain H in a reactor 2/ CO is than being the synthetic gas of 0.5-3.
For example, be particularly suitable for using in first kind of flow process of hydrocarbon gas reactant, especially Sweet natural gas, two reactions steps can be carried out at two different sites of autothermic reactor, and combustion reactions is carried out in the ingress of reactor; And conversion reaction is carried out in ensuing catalytic bed, and service temperature is 600 °-1000 ℃, preferably 700-850 ℃.Owing to adopted above-mentioned catalyzer, only use an autothermic reactor, and the service temperature of this reactor is hanged down 200 ℃ approximately than the temperature (800-1000 ℃ and 2-4MPa) of the self-heating conversion reactor that adopts at present, can obtain synthetic gas under high transformation efficiency.
Pressure in burning and the conversion reactor can change in the scope of 0.05-6MPa, preferably 0.1-5MPa.Comparatively speaking, in second kind of flow process, two reactions steps are to carry out in two different reactors.Carry out catalysis or non-catalytic combustion reactions in first reactor, second reactor utilizes the first reactor combustion heat and the product, carries out catalytic conversion reaction, can add also not add more combustible gas.
If combustion reactions proceeds to reactant and all changes into CO 2And H 2O, the product of combustion reactions mixed (carbonatoms is no more than 10) with lighter hydrocarbons before entering the conversion reaction bed.
In order to describe the present invention better,, but should understand that the present invention is not subjected to the restriction of these embodiment or is not limited to them now for several embodiment.
Embodiment 1
Methane and AIR MIXTURES enter in the reactor that refractory materials is housed.In the ingress of reactor, a gas stream burning device is arranged.Behind the combustion zone that reaction (1) takes place, a ring-type catalytic bed is arranged.In this bed, (2) and (3) react.Insert a thermopair at the beds center, be used for the assaying reaction temperature.Filling 20ml catalyzer in reactor.Enter in the mixture of reactor CH 4/ O 2Than equaling 2.The air speed of adjustments of gas, making the temperature in the beds of conversion reaction is 750 ℃, air speed is 11000hr -1, after reaching stable reaction conditions, carry out 100 hours catalyst test.
Used catalyzer follows these steps to prepare in the conversion reaction:
Under stirring condition, be 210m with specific surface 2The industrial magnesium oxide of/g (Carlo Erba provides) is suspended in tetraethyl silicane acid esters (TES) solution.Temperature is remained on 80 ℃-90 ℃, and this alcoholic acid that will help to generate because of condensation reaction evaporates.Dry nitrogen stream passes through reaction environment.The gas chromatographic analysis result of exit gas shows and has generated ethanol.When from exit gas, no longer detecting ethanol, think that promptly condensation reaction finishes.At this moment, temperature is raised to 180 ℃, steams unreacted tetraethyl silicane acid esters.The unreacted ethoxy group that is connected on the Siliciumatom, is fixed on again on the inoganic solids then flows by adding nitrogen and water vapor down at 200 ℃, makes it hydrolysis.This step also can detect ethanol in air-flow.Then, the material that is obtained is carried out Infrared spectroscopy, the result shows have the hydroxyl bond that does not have in many raw materials to exist.Then, solid is heated to 850 ℃ (5 ℃/min), and under this temperature, kept 10 hours.After these operations were finished, specific surface reduced to 32m 2/ g, and the weight percentage of silicon is 1.5%.In three heat cycles of 25-750 ℃, carry out differential thermal analysis, thermogravimetric analysis and Infrared spectroscopy.The result shows that thus obtained silication material does not have significant change on chemistry and physical properties.At this moment, under nitrogen environment, with 50g silication magnesium hydroxide suspension in the 2-of 100ml methylpentane.Under stirring condition, with same solvent, contain 0.091gRh 4(CO) 12Second kind of solution of 50ml in CO atmosphere, be added drop-wise to rapidly in the silicide oxide suspension.Organic solution is become colorless by scarlet rapidly, simultaneously the white solid band look that becomes.Under inert atmosphere, filter, obtain a kind of 0.1%(of containing weight) material of Rh.Rh is a high dispersing, and this point can clearly be found out from the carbonyl vibrational band analysis of surface complex.
Leave the gas gc analysis of reactor.The transformation efficiency of oxygen is 100%, and methane conversion is 62%.Leave in the gas of reactor H 2/ CO ratio is 1.92.
If disregard nitrogen, the composition of product sees Table 1.Between the reaction period, do not observe the deactivation phenomenom of catalyzer.
Table 1
CH 4＝8.0%
CO 2＝3.1%
H 2O＝2.1%
CO＝29.8%
H 2＝57.0%
Embodiment 2-5
CH 4Enter the tubular type quartz reactor with AIR MIXTURES.This reactor wraps up with refractory materials, has two with porous diaphragm separated catalyst bed.Come control reaction temperature with electric furnace.Add the 5ml combustioncatalysts in first beds, it is 0.1% metal Rh that this catalyzer contains weight, and Rh is deposited on the silicon-dioxide.In second beds, add the 10ml catalyzer, this catalyzer contains 0.1%(weight) metal Rh, Rh is deposited on the aluminum oxide (preparation method is identical with embodiment 1) of silication.Four thermopairs are inserted in place at gas turnover beds, measure the temperature during burning and the conversion reaction.At 500 ℃-800 ℃, by four kinds of different CH are provided 4/ O 2The mixture of ratio has carried out catalytic test four times.Leave the gas composition gas chromatography determination of reactor, the result is shown in Fig. 1-4.Four kinds of CH 4Enter the methane conversion that reactor obtains with air mixture and be shown in Fig. 5.
Embodiment 6
In two different reactors, carry out combustion reactions (1) and the water vapor and the CO of heat release 2The thermo-negative reaction (2) and (3) that transform.
Fig. 6 is the experimental installation synoptic diagram.
In first quartz reactor (R1), carry out total catalyst combustion reaction, catalyzer 5g contains 0.5%(weight) platinum, by immersion deposition on aluminum oxide.The long 5cm of beds, flow of feed gas (CH 4And air) with 5000hr -1Air speed (gas hourly space velocity) process.CH in the charging 4With air through mixing, make O 2/ CH 4Than equaling the 2.5(volume), the temperature out of beds is controlled at below 550 ℃.Air-flow leaves the temperature maintenance of first reactor at 350 ℃, reacts (2) and (3) before entering second reactor (R2), again with CH 4Mix, and stratographic analysis.Gas composition at the second reactor inlet place is:
Volume %
CH 418.2
CO 26.1
H 2O 12.1
O 23.0
N 260.6
Filling 5g catalyzer in second reactor, this catalyzer contains 0.1%(weight) Rh, Rh is deposited on (preparation method is with embodiment 1) on the silication magnesium oxide.In long 5cm second reactor of beds, the air speed of air-flow is 10000hr -1The gas flow temperature of leaving beds maintains 800 ℃.
Under these conditions, the flow groups in the outlet of second reactor becomes:
Volume %
CH 41.1
CO 21.0
H 2O 5.5
O 2-
N 245.5
CO??16.9
H 230.0
At 1000 hours duration of test of catalyzer, do not observe deactivation phenomenom.
(in the synoptic diagram of Fig. 6, marked:
Water cooler A
Water cooler B
Burner C
Gasometry D)

Claims (19)

1, a kind of being used for from the method for hydrocarbon production synthetic gas, it is characterized in that, it carries out in one or more reactors by two reactions steps, in first reactions steps, carry out the combustion reactions of heat release, hydrocarbon or hydrocarbon mixture or carbon and air and/or oxygen are reacted, and available usually following principal reaction is described:
In second reactions steps, the heat that utilizes combustion reactions to produce carries out conversion reaction, make the product of combustion reactions and carbonatoms be no more than 10 hydrocarbon or hydrocarbon mixture basically and react under the catalyst system effect, the principal reaction below available usually is described:
This catalyst system contains:
-one or more platinum group metal compounds;
-a kind of carrier of being made up of mineral compound, the weight percent of platinum metals is 0.01-20% in the catalyst system.
2, according to the process of claim 1 wherein that the weight percent of platinum metals is 0.05-3%.
3, according to the process of claim 1 wherein platinum metals selected from rhodium, ruthenium, palladium and platinum.
4, according to the process of claim 1 wherein that specific surface is at 1-400m 2Change between/the g, and pore volume is between 0.1-3ml/g.
5, according to the method for claim 4, wherein surface-area is at 10-200m 2Change between/the g, and pore volume is between 0.5-20ml/g.
6,, become mutual bonded form to exist with itself form according to the process of claim 1 wherein that the mineral compound that constitutes carrier is selected from the oxide compound and/or the spinel of aluminium, magnesium, zirconium, silicon, cerium and/or lanthanum.
7, according to the method for claim 6, wherein the oxide compound of aluminium, magnesium, cerium or lanthanum is by silication.
8, according to the method for claim 6, wherein carrier contains basic metal.
9, adopt one or more catalyzer to carry out combustion reactions according to the process of claim 1 wherein.
10, according to the method for claim 9, wherein catalyzer is selected from the Pt that is stated from silicon-dioxide and/or the aluminum oxide, Pd, Rh, Cu, Ag.
11, according to the method for claim 9, wherein catalyzer is selected from TiO 2, V 2O 3, Cr 2O 3, MnO 2, Fe 2O 3, Co 3O 4, NiO, CuO, ZnO.
12, according to the method for claim 9, the similar catalyzer that is used for conversion reaction of catalyzer wherein.
13, according to the process of claim 1 wherein the burning and conversion reaction in single reaction vessel, carry out.
14, according to the method for claim 13, wherein used single reaction vessel is operated under 600-1000 ℃ and 0.05-6MPa.
15, according to the method for claim 14, wherein temperature is between 700-850 ℃, and pressure is between 0.1-5MPa.
16, according to the process of claim 1 wherein that conversion reaction carries out in single reaction vessel.
17, according to the method for claim 1 and 16, wherein burning and conversion reaction are carried out in two reactors.
18, basis the process of claim 1 wherein that the combustion reactions of heat release is performed until all reactants and all changes into CO 2And H 2O.
19, according to the method for claim 18, wherein the product of heat release combustion reactions mixed with lighter hydrocarbons before entering the beds of conversion reaction.
CN91108515A 1990-08-29 1991-08-28 A kind of catalysis process by hydrocarbon conversion and combustion reactions production of synthetic gas in next life Pending CN1059318A (en)

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