CN1061164A - The catalyzed selective oxydehydrogenation of methane - Google Patents
The catalyzed selective oxydehydrogenation of methane Download PDFInfo
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- CN1061164A CN1061164A CN91109095A CN91109095A CN1061164A CN 1061164 A CN1061164 A CN 1061164A CN 91109095 A CN91109095 A CN 91109095A CN 91109095 A CN91109095 A CN 91109095A CN 1061164 A CN1061164 A CN 1061164A
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- transition metal
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 64
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 37
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 17
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- 150000003818 basic metals Chemical class 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 239000010419 fine particle Substances 0.000 claims 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 34
- 230000009466 transformation Effects 0.000 abstract description 12
- 230000004913 activation Effects 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 5
- 235000010333 potassium nitrate Nutrition 0.000 description 5
- 239000004323 potassium nitrate Substances 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- -1 hydrogen oxide compound Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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Abstract
Disclose a kind of new catalyst that is used for the lower hydrocarbon oxidative coupling is become higher hydrocarbon, this catalyzer contains alkaline earth metal oxide, transition metal oxide and small amounts of alkali metal oxides.Also disclose having under the condition of steam, made C with this new catalyst
1Be selectively converted to C
2Oxidative coupling method with higher hydrocarbon.Use this method, can obtain 100% selectivity, transformation efficiency and productive rate are at least 8%.
Description
The present invention relates to hydrocarbon, particularly the oxidative coupling method and the catalyst composition of methane more precisely, the present invention relates to make C having under the condition of steam with new catalyst
1Optionally be converted into C
2Oxidative coupling method with higher hydrocarbon.Use this method, can obtain 100% selectivity, transformation efficiency and productive rate are at least 8%.
The present invention is according to the contract DE-ACO3-76SF00098 between USDOE and the Gary Fu Niya university, experimentizes in Lawrence Berkely laboratory at contract period and makes.According to this contract, United States Government has certain right to the present invention.
Long-term come, chemical industry is thought and is used C
1It is very valuable that raw material (particularly methane) is produced senior long chain hydrocarbon, main because, usually can earlier the methane-rich gas that is obtained by Sweet natural gas be converted into senior gaseous state or liquid hydrocarbon, available then its provides other reagent of synthetic liquid fuel and chemical industry.
This is the target that many researchists lay siege to.There are a lot of documents to relate to this theme.Many methods are provided in the document, have comprised the method for carrying out catalyzed conversion with various different catalysts.Really, might make C today
1Be converted into senior long chain hydrocarbon.Yet, so far, think that these methods have a lot of shortcomings, comprise uneconomical, produce a large amount of pollute and processing parameter nonconforming.
At C
1Oxidative coupling in, mainly the parameter that should consider is selectivity, transformation efficiency and productive rate.CO and CO
2Formation be to influence C
2The principal reaction that hydrocarbon forms.Term " selectivity " expression requires the C of formation
2, C
3Or C
4Product C
2+Account for the C of total conversion
1The percentage ratio of material.Therefore low selectivity means a large amount of CO of generation in reaction process
XCO
XGeneration represent C
1The two all reduces reactant and oxygen, and this is very serious equally, because CO
XBe undesirable pollutent, therefore, require to use alkaline solution, it is removed from unconverted round-robin methane by washing.
Term " transformation efficiency " is used for representing that one way passes through the C that has reacted of reactor
1The percentage ratio of raw material.Be that transformation efficiency is unreacted C in the product stream
1The C that exists in inventory and the initial stream
2Inventory poor.Reaction product in the oxidative coupling process is C
2(with senior) hydrocarbon, water and CO
XUsually, the amount of conversion is the function of specificity of catalyst, reactor and process variable, and therefore, transformation efficiency changes slightly with flow velocity, catalytic amount, temperature of reaction etc.Usually, to the technology known and practical reactor transformation efficiency less than about 50%.Therefore, in actual device, always need product is passed through reactor cycles.Because CO
XIncrease and influence to react, therefore, all coupling processes of low selectivity parameter are arranged, comprise all oxidative coupling processes of knowing so far, should be provided with and remove CO
XStep.
By product selectivity and transformation efficiency definition " productive rate ", this parametric representation is in given reactor, under given operational condition, by initial material C
1The desired C that forms of amount
2Or the percentage ratio of the amount of higher hydrocarbon products.
Certainly, the significant parameter of evaluation common response process is C
2And/or the relative productive rate of higher hydrocarbon.Yet, be important to note that, total from the viewpoint of expense, even it is superior to reach 100% processing method that obtains high yield and high conversion that optionally processing method is lower than selectivity.
Therefore, main purpose of the present invention provides a kind of method of methane oxidative coupling, it is characterized in that C
2With higher hydrocarbon higher selectivity is arranged.
Another object of the present invention provides and a kind ofly can suppress CO to greatest extent
XTherefore the oxidative coupling method that forms there is no need to remove CO fully
X
The present invention also has another purpose to provide a kind of promotes oxidn coupling, selectivity height, and the catalyzer produced again easily.
The present invention also have the another one purpose provide a kind of aspect the requiring of reagent more economical method, it makes the consumption of oxygen and steam reduce to minimum, therefore, this technological process can safety be carried out under flammability limit.
By following description and accompanying drawing, for a person skilled in the art, these and other purposes of the present invention and advantage comprise that the ability that can operate under than the low temperature of the method for other propositions will become clearly.
The present invention is a short hydrocarbon, the oxidative coupling method of methane particularly, this method is under the about 500-650 of lesser temps ℃, with methane and steam and a small amount of oxygen together by basic metal, the catalyzer of alkaline-earth metal and transition metal oxide.In the material gas mixture, methane: oxygen: the optimum mole ratio of water is about 3: 1: 6.5, and pressure is normal atmosphere-Yue 500Psig.
The present invention be more particularly directed to catalyst composition and preparation method thereof.Usually, selectivity of catalyst of the present invention is higher than the catalyzer of prior art, and promptly 80% or higher, the preferred selectivity of catalyst of the present invention can reach 100% basically.Yet, in this scope, chemical constitution and preparation method that optimum catalyst activity that reaches and selectivity depend primarily on catalyzer.Preferred catalyzer is the hopcalite that the atomic wts ratio is about 2: 1: 0.01 calcium, nickel and potassium.
Catalyzer be by under the temperature that improves at the aqueous solution of air drying, decomposition and oxidation blended nitrocalcite and nickelous nitrate, and add a small amount of saltpetre in reaction process and make.
Also available similar methods makes optimum catalyst by corresponding oxyhydroxide.
Usually, the catalyzer that catalyzer of the present invention is better than knowing so far, particularly their selectivity.Yet the most outstanding aspect of the present invention is to find can to obtain 〉=the 99%+ selectivity with catalyzer of the present invention, owing to so oxidable coupling methane of catalyzer but do not produce CO
X, therefore, before need or not reclaiming in circulation from product flows separation of C O
XBelow these catalyzer that belong to main preferred catalyst scope are discussed.
Begin to illustrate the characteristic of catalyzer and the mechanism of oxidative coupling now.When not understanding fully in this, opposite with most of reported in literature, it seems that coupled reaction occurs in catalyst surface, and do not comprise gas-phase reaction.Paralleling reactor turnover carbon balance studies show that between the reaction under-stream period carbon loss is arranged in reactor.It is believed that this carbon laydown on catalyzer, and good as if play an active part in catalytic process.
In the steam oxidation coupling process of methane, the catalyst composition that obtains selectivity=100% is the mixture of the activating oxide of specified the atomic ratio calcium, nickel and the potassium that were about 2: 1: 0.1.
Though, permit a small amount of CO
XExist, even but only account for few per-cent and also do not require, because, under the round-robin situation, CO
XAmount increases, and requires reactor effluent is purified.Catalyst composition can followingly change: Ca/Ni is than about 2: about 4: 1 of 1-, Ni/K is than about 1: about 1: 0.2 of 0.05-.
As mentioned above, the Preparation of catalysts method requires the catalyzer of characteristic to play an important role to obtaining.Have found that, use following method, can obtain the catalyzer of selectivity 〉=99%+ usually.
Catalyzer can be made by the aqueous solution of nitrocalcite, nickelous nitrate and saltpetre.In addition, catalyzer also can be made by oxyhydroxide or carbonate.It seems that importantly the negatively charged ion of solution is identical.The most handy nitrate aqueous solution prepares catalyzer.By same quadrat method, available hydrogen oxide compound or carbonate prepare catalyzer.
According to the high density of solubleness permission, the preparation nitrate aqueous solution mixes an amount of solution the Ca/Ni ratio that obtains requiring.Can be such as described below, an amount of saltpetre is mixed at this moment, or mix afterwards.Then, blended solution is dry and decompose in about 700 ℃ of air, form corresponding oxide compound.
In addition, potassium nitrate solution can be added in the mixture of dry and the calcium that decomposes and nickel oxide, then, complete drying and decomposition in 700 ℃ of air are up to forming pulverulent mixture.This catalyzer can powdery uses, or mold pressing or be squeezed into granular use.
Have found that it is satisfied that DNAcarrier free catalyzer is used for reactor.But, can require to use inert support, for example, the Al of porous ceramics
2O
3Or SiO
2, increasing surface-area, and allow raw material with high-speed or high transform pass through catalyzer.In order to prepare carried catalyst, solid support material can be added in the dry preceding solution mixture, then, process like that by described.
Catalyzer before use must activation.The activation of catalyzer can be finished before catalyzer adds reactor, or is preferably in and puts into the reactor aftertreatment, but must carry out before being exposed to raw material.For active catalyst, catalyzer should for example be exposed to that speed is about 2CCO under about 680 ℃ of temperature
2In the Oxygen Flow or airflow of/g catalyzer.
The time of catalyst activation as shown in table 1 below is very important, and long soak time increases transformation efficiency, also increases the special selectivity to long chain hydrocarbon, and influences the ratio of olefin/paraffin.Therefore, to have the methane conversion of making be C to catalyzer of the present invention
3And C
4The key property of hydrocarbon, and the activation step of catalyzer provides a kind of best approach for producing the hydro carbons that requires.
The research and the test of reaction mechanism show, when the catalyzer of above-mentioned special formulation obtains near 100% selectivity, illustrate that the catalyzer of the general type that the composition by alkaline earth and transition metal oxide and small amounts of alkali metal oxides constitutes can make selectivity obviously improve.So-called " on a small quantity ", we are meant less than 1/20 of gross weight, or about 1/20-about 1/100.More precisely, the preferred alkaline-earth metal of catalyzer of the present invention comprises magnesium, calcium and barium; Preferred transition metal is iron, cobalt and nickel; Preferred basic metal is lithium, sodium and potassium.The mol ratio of preferred alkaline-earth metal/transition metal is about 2: about 4: 1 of 1-, preferred transition metal/basic metal mol ratio is about 1: about 1: 0.2 of 0.05-.
Prepare these preferred catalyzer with described with quadrat method, and with they activation, promptly, with metal and equate anionic soluble salt, nitrate preferably, the original mixture of carrier substance or carrier free material is at 650 ℃ of-750 ℃ of air dryings, make nitrate be converted into oxide compound, then, under about 700 ℃, use about 48 hours of oxygen activation 1-.
According to research, we think, except described Preparation of catalysts method so far, following factors plays an important role to catalyzer: material balance is measured and is shown, the carbon deficit takes place in the stage that goes into operation at oxidative coupling, and we think that this is owing to the result of carbon laydown at catalyst surface.Table 2 shows, move about 3 hours after, just can reach 100% material balance.
Table 2
| Time (branch) | Carbon balance % |
| 25 | 70 |
| 50 | 95 |
| 100 | 98 |
| 200 | 100 |
| 400 | 100 |
In addition, water is very big to the influence of oxidative coupling.On this meaning, in reaction process,, totally unfavorable to selectivity if replace water with rare gas element.The data of table 3 show, when operation, replace steam with helium, and the selectivity and the transformation efficiency of hydrocarbon significantly descend, and when replacing helium again with steam, and return to original value.
Table 3
| The time (branch) of logical steam | Temperature (℃) | Thinner | Hydrocarbon-selective % | Methane conversion % | Hydrocarbon productive rate % |
| 85 | 600 | Steam | 100 | 9.5 | 9.5 |
| 200 | 600 | Helium | 75 | 5.0 | 3.8 |
| 300 | 600 | Helium | 15 | 2.1 | 0.3 |
| 400 | 600 | Steam | 90 | 11.0 | 9.9 |
Active and inactive catalyst research is shown that the catalyst NiO less with activity compares with the X-ray emission, to active catalyzer, signal and Ni(OH)
2More the Ni of high oxidation state is relevant.
With reference now to Fig. 1,, the service condition of above-mentioned catalyzer in hydrocarbon coupling process discussed.Fig. 1 represents to be used to study testing apparatus of the present invention briefly.The aspect that the present invention gives prominence to is to be ethane and ethene with methane conversion, still, as discussed above, also forms higher hydrocarbon, and according to the situation of catalyst pretreatment, the conversion rate that higher hydrocarbon can be higher forms.The hydro carbons that this method also can be used for comprising methane and long-chain olefin or alkane is coupled to the more hydrocarbon of long-chain, for example, comprises C
3-C
10
Coupled reaction is carried out in reactor 10, it comprise by around be the catalyst container 11 of heating unit 12, the temperature of reactor can be regulated, and can maintain required value.Usually, reactor is equipped with instrument, with temperature regulator 13, temperature sensor 14, pressure warning unit 15 with mass flow controller 16 measures and control pressure, temperature and flow velocity.
Flow into spreader 24 from exporting 23 effusive products.Water is separated in water susceptor 25.Owing in production unit, use selectivity to be lower than 100% catalyzer, therefore require to remove CO
X, circulation loop also must be equipped conventional washer and be used to remove CO
XWith incidental analyser analysis and check product.As shown in the figure, in order to supply with known quantitative mixture 29, analyser comprises the chromatographic instrument 26 that has holder 27 and band valve pipeline 28.In operating process, catalyzer is put into reactor, and activation as stated above.Available two catalyst chambers in the reactor so that raw material alternately carries out operate continuously by two catalyst chambers, promptly when raw material when a catalyst chamber is handled, and in another catalyst chamber the dress catalyzer and the activation.Certainly, catalyzer can be as mentioned above, at the reactor front activating of packing into.Behind catalyst activation, allow temperature of reactor be raised to about 550-650 ℃.Produce about 140 ℃ steam by heating duct 21, and methane, oxygen and steam are introduced reactor.The composition of raw material is with CH
4/ O
2/ H
2The mol ratio of O represents that it is 2/1/4-5/1/8, and optimum mole ratio is about 3/1/6.5.Should be noted that this process is to carry out below the limits of explosion of methane and oxygen.It is generally acknowledged that major advantage of the present invention is to use steam, the requirement of oxygen is reduced and operation (method of introducing in the document is 705-900 ℃ of operation) under lower temperature, also is convenient to safety operation.
Preferred raw material flow rate is about 40 mole of methane/gram catalyzer hour.As mentioned above, in the reaction initial stage, the material balance of carbon shows that catalyzer absorbs about 3 hours of carbon.Fig. 2 is the graphic representation of material balance and timing relationship.In at least two days operation, in case reach 100% carbon balance, catalyst life is long, and the hydrocarbon productive rate is constant.In warm, can produce a small amount of permissible CO
XBlank test shows, CO
2Be by the gas-phase reaction deposits yields of preheating zone, rather than because the low cause of catalyst selectivity.To make comparisons with the inactive ceramic particulate with the blank test that catalyzer carries out shows, in fact catalyzer can reduce the methane gas inversion of phases and becomes CO
2
Fig. 3 shows when temperature and is increased to 750 ℃ from 600 ℃, and then when dropping to 600 ℃, Ca/Ni/K=2: the changing conditions of 1: 0.1 selectivity of catalyst, transformation efficiency and productive rate.By on can find out that selectivity is from 100% initial surprising dropping to＜10%, when temperature was returned to 600 ℃ again, selectivity was returned to again＞90%.
Embodiment
Embodiment 1:
By nitrate solution at air drying calcium and nickel, in 700 ℃ of air, make nitrate resolve into oxide compound, make and contain the catalyzer that atomic ratio is the oxide compound of 2: 1 calcium and nickel, under 680 ℃, activation is 20 hours in Oxygen Flow with catalyzer.Then catalyzer being put into reactor, under 600 ℃ and normal atmosphere, is 3: 1: 6.5 CH with mol ratio
4, O
2With the gaseous mixture of water, with 40 moles of CH
4The speed of/gram catalyzer hour is passed through catalyzer.Work as CH
4Transformation efficiency is about 10%, C
2And C
3Productive rate is 8% o'clock, and the selectivity to higher hydrocarbon in the product is about 80%.
Embodiment 2:
By at air drying C
aAnd N
iNitrate solution, in 700 ℃ of air, make nitrate resolve into oxide compound, add potassium nitrate solution again, again 700 ℃ down dry and decompose, make and contain the catalyzer of oxide compound that atomic ratio is 2: 1: 0.1 calcium, nickel and potassium.Under 600 ℃, activation is 20 hours in Oxygen Flow with catalyzer.Work as CH
4, O
2With the mol ratio of water be 3: 1: 6.5 mixture, under 600 ℃ and normal atmosphere with 40 moles of CH
4The speed of/gram catalyzer hour is during by catalyzer, and methane conversion is about 11%, C
2+Productive rate is 11%, in the product to C
2+The selectivity of hydrocarbon reaches 100%.
Embodiment 3:
With embodiment 2 described methods, preparation contains the catalyzer of oxide compound that atomic ratio is 4: 1: 0.1 calcium, nickel and potassium.The transformation efficiency of this catalyzer is identical with the catalyzer of embodiment 2 with selectivity.
Embodiment 4:
What will make by the method for embodiment 2 contains the catalyzer that atomic ratio is the oxide compound of 2: 1: 0.1 Ca, Ni and K, and activation is 1 hour in 700 ℃ of Oxygen Flow.Under embodiment 1 described condition, this catalyzer is carried out the oxidative coupling test of methane, work as CH
4Transformation efficiency is 2% o'clock only, to C
2+The selectivity of hydrocarbon is 100%.To C
2The selectivity of hydrocarbon is 98%, to C
3The selectivity of hydrocarbon is 2%.C
2+The ratio of the olefin/paraffin of hydrocarbon is 0.2.
Embodiment 5:
The catalyzer that will make by the method for embodiment 2 is at 680 ℃ of O
2Activation is 40 hours in the air-flow.Under embodiment 1 described condition, this catalyzer is carried out the oxidative coupling test of methane.Work as CH
4Transformation efficiency is 9.5% o'clock, to C
2+The selectivity of hydrocarbon is 100%.To C
2The selectivity of hydrocarbon is 86%, to C
3The selectivity of hydrocarbon is 11%, to C
4The selectivity of hydrocarbon is 3%.The ratio of olefin/paraffin is 0.8.
Obviously, with reference to the above-mentioned description of this invention, those skilled in the art can make various improvement, but all be unable to do without the spirit and scope of the present invention, and therefore, scope of the present invention is only limited by following claim.
Claims (19)
1, a kind of catalyzer that is used for the lower hydrocarbon oxidative coupling is become higher hydrocarbon, it comprises: alkaline earth metal oxide, transition metal oxide and small amounts of alkali metal oxides.
2, the catalyzer of claim 1, wherein said alkaline-earth metal is selected from magnesium, calcium, strontium and barium.
3, the catalyzer of claim 1, wherein said transition metal chosen from Fe, cobalt and nickel.
4, the catalyzer of claim 1, wherein said basic metal are lithium, sodium or potassium.
5, the catalyzer of claim 1, wherein alkaline-earth metal is about 2 to the atomic ratio of transition metal: 1-4: 1, transition metal is about 1 to alkali-metal atomic ratio: 0.05-1: 0.2.
6, the catalyzer of claim 1, wherein catalyzer at high temperature is exposed in the oxygen and activates 1-48 hour.
7, the catalyzer of claim 6, wherein temperature is 700 ℃.
8, the catalyzer of claim 1, wherein this catalyzer is by comprising the aqueous solution of described alkaline-earth metal, transition metal, basic metal and identical anionic salt, the described solution of heating is to doing in air, decomposes and the described alkaline-earth metal of oxidation, transition metal and basic metal and make.
9, the catalyzer of claim 8, wherein said negatively charged ion are nitrate radical or hydroxide radical.
10, the catalyzer of claim 1, wherein said catalyzer is placed on the surface of porous fine particle, inert base.
11, the catalyzer of claim 1, wherein said catalyzer is granular.
12, a kind of catalyzer of hydrocarbon oxidative coupling comprises the hopcalite of calcium, nickel and potassium.
13, the catalyzer of claim 12, wherein the mol ratio of calcium and nickel is about 2: 1-4: 1, the mol ratio of nickel and potassium is about 1: 0.05-1: 0.2.
14, a kind of is alkane and C with methane conversion
2, C
3And C
4The method of alkene and selectivity about 80% is under 500-600 ℃ of temperature and normal pressure-500Psig pressure, with the catalyzer of the composition of methane and oxygen and the steam mixture oxide compound by containing alkali, alkaline earth and transition metal.
15, according to the method for claim 14, wherein catalyzer comprises the composition of the oxide compound of calcium, nickel and potassium.
16, according to the method for claim 14, wherein catalyzer comprises that atomic ratio is about the composition of the oxide compound of 2: 1: 0.1 calcium, nickel and potassium, and this catalyzer is before conversion reaction, under 700 ℃ of Oxygen Flow oxidation 1-48 hour.
17, according to the method for claim 14, wherein catalyzer comprises the composition of the oxide compound of magnesium, iron and sodium.
18, the method for claim 14, wherein the mol ratio of methane, oxygen and steam is 2: 1: 4-5: 1: 8.
19, the method for claim 18, wherein the mol ratio of methane, oxygen and steam is about 3: 1: 6.5, temperature is about 600 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57040890A | 1990-08-21 | 1990-08-21 | |
| US570,408 | 1990-08-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1061164A true CN1061164A (en) | 1992-05-20 |
Family
ID=24279533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91109095A Pending CN1061164A (en) | 1990-08-21 | 1991-08-20 | The catalyzed selective oxydehydrogenation of methane |
Country Status (7)
| Country | Link |
|---|---|
| CN (1) | CN1061164A (en) |
| AU (1) | AU8529091A (en) |
| CS (1) | CS258691A3 (en) |
| MA (1) | MA22262A1 (en) |
| MX (1) | MX9100757A (en) |
| WO (1) | WO1992003225A1 (en) |
| ZA (1) | ZA916611B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049611C (en) * | 1993-03-22 | 2000-02-23 | 吉林大学 | Ceramic fibre loaded high temperature reaction catalyst |
| CN1054114C (en) * | 1997-03-12 | 2000-07-05 | 天津大学 | Electric field enhanced plasma catalytic synthesis of C2 hydrocarbon with natural gas |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7812201B2 (en) | 2008-10-01 | 2010-10-12 | Targa Resources, Inc. | Process and catalyst for converting alkanes |
| EP3529609A2 (en) * | 2016-10-21 | 2019-08-28 | SABIC Global Technologies B.V. | Stable catalysts for oxidative coupling of methane |
| CN114713282B (en) * | 2021-01-05 | 2023-08-04 | 中国石油化工股份有限公司 | Modification method of catalyst for preparing olefin from methanol |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3402022A (en) * | 1965-01-04 | 1968-09-17 | Universal Oil Prod Co | Method for producing hydrogen and a catalyst therefor |
| US4009126A (en) * | 1974-02-19 | 1977-02-22 | Petro-Tex Chemical Corporation | Catalyst for removing acetylenic impurities |
| US4450310A (en) * | 1983-03-04 | 1984-05-22 | The Standard Oil Company | Conversion of methane to olefins and hydrogen |
| JPH0674215B2 (en) * | 1987-12-11 | 1994-09-21 | 宇部興産株式会社 | Hydrocarbon production method |
| US4956327A (en) * | 1989-05-31 | 1990-09-11 | Institute Of Gas Technology | Mixed basic metal oxide/sulfide catalyst |
-
1991
- 1991-08-20 CN CN91109095A patent/CN1061164A/en active Pending
- 1991-08-21 MA MA22543A patent/MA22262A1/en unknown
- 1991-08-21 WO PCT/US1991/005779 patent/WO1992003225A1/en active Application Filing
- 1991-08-21 AU AU85290/91A patent/AU8529091A/en not_active Abandoned
- 1991-08-21 MX MX9100757A patent/MX9100757A/en unknown
- 1991-08-21 CS CS912586A patent/CS258691A3/en unknown
- 1991-08-21 ZA ZA916611A patent/ZA916611B/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049611C (en) * | 1993-03-22 | 2000-02-23 | 吉林大学 | Ceramic fibre loaded high temperature reaction catalyst |
| CN1054114C (en) * | 1997-03-12 | 2000-07-05 | 天津大学 | Electric field enhanced plasma catalytic synthesis of C2 hydrocarbon with natural gas |
Also Published As
| Publication number | Publication date |
|---|---|
| AU8529091A (en) | 1992-03-17 |
| MX9100757A (en) | 1992-04-01 |
| WO1992003225A1 (en) | 1992-03-05 |
| MA22262A1 (en) | 1992-04-01 |
| CS258691A3 (en) | 1992-04-15 |
| ZA916611B (en) | 1992-05-27 |
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