CN1764501A - Low coke formation catalyzer and reforming method and production for synthesis gas - Google Patents

Low coke formation catalyzer and reforming method and production for synthesis gas Download PDF

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CN1764501A
CN1764501A CNA038262606A CN03826260A CN1764501A CN 1764501 A CN1764501 A CN 1764501A CN A038262606 A CNA038262606 A CN A038262606A CN 03826260 A CN03826260 A CN 03826260A CN 1764501 A CN1764501 A CN 1764501A
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metal oxide
size
nickel
catalyst
composition
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G·J·刘易斯
J·E·鲍尔
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Honeywell UOP LLC
Universal Oil Products Co
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Abstract

Applicants have developed a novel catalyst composition comprising a crystalline metal oxide having the empirical formula: AvBt+wNixD(Gu-)yOz, where A is an alkali metal (e.g. Na), B is a basic metal (e.g. Ca), D is a framework component (e.g. P), and G is an anionic species (e.g. OH-). Nickel may be present in the framework of the crystalline metal oxide, dispersed thereon, or both. Preferably, the metal oxide component has an apatite or hydroxyapatite crystal structure. These crystalline metal oxide components have been found to have improved performance in partial oxidation and light hydrocarbon (e.g. methane) reforming to produce synthesis gas. A new process for synthesizing these metal oxides is also disclosed.

Description

Low coke forms the production of catalyst and reforming method and synthesis gas
Background technology
The present invention relates to a kind of new carbon monoxide-olefin polymeric, a kind of method and a kind of hydroconversion process that uses said composition for preparing said composition, above-mentioned composition contains the crystalline catalysts of phosphate base or vanadic acid alkali, nickel has mixed in the skeleton of crystallization metal oxide or has been deposited on the surface, or haves both at the same time.This catalyst is used for by light hydrocarbon (as methane) production of synthetic gas in next life.
Known available gas as synthetic gas or synthesis gas, is converted into by methane and light hydrocarbon and contains CO and H 2Mixture and make.Traditional synthesis gas generation method comprises gas-phase partial oxidation method (US-A-5292246), self-heating recapitalization method (US-A-5492649) and relates to CO 2Or various other methods of steam reformation.Selection to concrete route depends primarily on required product composition, and this composition depends on the purposes that it is final.Synthesis gas is generally used for producing methyl alcohol, ammonia, or by Fischer-tropsch process producing heavy mass hydrocarbon in next life fuel.
The partial oxidation of hydrocarbon can adopt a plurality of paths usually, and this depends on hydrocarbon and the relative scale of oxygen and the used process conditions of having reacted.Under the situation of methane, following reaction equation is possible:
(-64kcal/g mol CH 4)
(-34.9kcal/g mol CH 4)
Perhaps
(-5.7kcal/g mol CH 4)
With regard to the output of synthesis gas and make heat release minimize to avoid with regard to the cause thermal damage that a last reaction is optimal with protective device and beds.This path also when increasing hydrogen and carbon monoxide output, has correspondingly reduced the growing amount of steam.When this reaction takes place with reforming reaction, can provide high-quality syngas product.Therefore make carbon oxygen mol ratio (C: the O ratio) maximization in the feed gas mixtures can optimize partial oxidation reaction usually.Unfortunately, under high C: O ratio, the improvement that the formation of a large amount of cokings has often been offset the product quality aspect owing to limited the partial oxidation catalyst life-span.The result is that for giving reasonably stability of catalyst, usually need C: the O proportional limit has also just correspondingly improved the disposal cost in downstream under the numerical value that obtains the ideal product quality, for example with the relevant expense of the unconverted synthesis gas of circulation.
The self-heating recapitalization method makes methane and contains the oxygen charging mixes in diffusion flame and reacts.Effluent after the oxidation enters the steam reformation zone usually and contacts with the steam reforming catalyst of routine.Catalyst can comprise easy fixed bed or be immersed in component on monoblock carrier or the ceramic foam.It is active and stable through what use for many years that the high temperature in catalytic reforming zone is starved of reforming catalyst.The problem of catalyst coking need be operated under the condition inferior to optimum at feed composition and product quality usually in the self-heating recapitalization again.Particularly, in order to suppress coking, the steam injection rate must surpass only pays close attention to the amount of stipulating when optimizing product quality and making the communal facility cost minimization.For the control catalyst coke forms the C of steam reformation: H 2The C of O mol ratio and partial oxidation: O is than similar.Bigger ratio means higher coking trend usually.
According to the described self-heating vapour reforming of US-A-5492649, provide under the situation of a large amount of mixing points by thereby oxidizing gas is mixed methane gas at diffusion flame at injection nozzle place eddy flow with oxidizing gas, in the diffusion flame oxidation step, avoided generating a large amount of carbon or cigarette ash.Yet this method still makes and partial oxidation reaction can take place in the diffusion flame, caused the effluent of over oxidation and excessive temperature.The heat that generates can damage the surface of steam reforming catalyst and syringe.Disclosed Canadian patent application No.2153304 has instructed by reducing the molar feed ratio of steam and carbon, and the steam reformation temperature rises between 1100-1300 ℃, and/or increases the inlet amount of gaseous hydrocarbon, can reduce the generation of cigarette ash.
Using noble metal (as Pt) can reduce coke in the catalyst under very wide condition forms.In commercial Application, contain the expense of noble metal catalyst, cause usually in steam reformation, substituting and use the metal that is selected from uranium, VII family metal and group VIII metal, frequent and other metal of described metal, for example lanthanum and cerium are used in combination.Usually by the above-mentioned metal of heat-staple inorganic refractory oxide load.Preferred catalyst metals is the group VIII metal.Particularly suitable be nickel-containing material, especially nickel aluminum, nickel oxide and load on carrier are as the nickel on the Alpha-alumina.
The carrier material of particularly suitable comprises the plain film shape aluminium oxide of Alpha-alumina, aluminosilicate, cement, magnesia and fusion.Preferred catalyst carrier can be the Alpha-alumina of VII family metal oxide, rare earth oxide, modification, the oxide that contains Alpha-alumina, hexa-aluminate, calcium aluminate or magnesia aluminate.In some cases, binding agent can be used to rugged catalyst, for example the calcium aluminum oxide.Catalyst preferably contains the silica of minute quantity, for example less than 0.3 weight %, to avoid its volatilization and to pollute the equipment in downstream.The shape of catalyst carrier particle can change, and has comprised saddle type, star, pellet shapes, band spoke wheel shape and diameter, highly the Raschig ring shape in a 6-8mm hole has been arranged for 16mm, center.
US-A-3595808 discloses the dehydrogenation of phosphoric acid calcium nickel salt, wherein generates hydroxyapatite phase crystal in the process of the described catalyst of preparation.In this hydroxyapatite phase crystal, just there is one to be replaced in every 6-12 calcium atom by nickel.Brown and Constantz in hydroxyapatite and associated materials (Hydroxyapatite and Related Materials, CRC Press, Inc. (1994)), have described apatite structure, and its chemical general formula is A 10(BO 4) 6X 2, A is Ca, Sr, Ba, Pb, Cd and other rare earth element in the formula, BO 4Be PO 4 3-, VO 4 3-, SiO 4 4-, AsO 4 3-, CO 3 2-, and X is OH -, Cl -, F -, CO 3 2-Boechat, Eon, Rossi, Perez and Gil, at Phys.Chem.Chem.Phys., 2000,2, described the preparation and the structural characterization of calcium phosphate and vanadic acid calcium solid solution among the 4225-4230, and in composition, mixed Sr to generate Ca 10-xSr x(PO 4) 6-s(VO 4) s(OH) 2Apatite structure.Sugiyama, Minami, Higaki, Hayahi and Moffat be at Ind.Eng.Chem.Res.1997, and 36, to have described among the 328-334 in the presence of the strontium-incorporated hydroxyapatite of stoichiometric composition, methane conversion is a carbon monoxide.
Unexpectedly, the applicant finds that the coke that uses a kind of catalyst that contains the crystal metal oxide component can alleviate greatly in conventional oxidation and the reforming process forms problem, contains alkali metal (as Sr) and structural constituent (as PO in the described crystal metal oxide component 4Or VO 4), alkali metal not necessarily is positioned at crystalline framework.Active nickel is also included within the skeleton and/or is dispersed in the surface of crystal metal oxide component.The catalyst of the application of the invention in hydrocarbon oxidation and reforming process and reduce coke and form and to have overcome many foregoing problems that relate to performance constraint and correlative charges burden.
Summary of the invention
The present invention is used for comprising having chemical composition with based on anhydrous empirical formula from the embodiment that light hydrocarbon prepares the synthetic gas catalyst composition:
A v(B t+) wNi xD(G u-) yO z
The crystal metal oxide component of expression, wherein A is selected from Li +, Na +, K +, Rb +, Cs +Alkali metal and composition thereof; " v " is the mol ratio of A and D, and size is 0-2; B is an alkalinous metal; " w " is the mol ratio of B and D, and size is 1-3; " t " is the weighted average chemical valence of B, and size is 2-3; " x " is the mol ratio of Ni and D, and size is 0-0.5; D is selected from P + 5, V + 5And composition thereof the skeleton component; G is selected from OH -, Cl -, F -, CO 3 2-And composition thereof anion; " u " is the average valence of G, and size is 1-2; " y " is the mol ratio of G and D, and size is 0-2; " z " is the mol ratio of O and D, and its numerical values recited is determined by following formula:
z＝(v+t·w+2·x+5-u·y)
When B was Ca, " v " was not equal to 0, and when " x " was 0, carbon monoxide-olefin polymeric also comprised the nickel component that is dispersed on the crystal metal oxide component.
In a kind of preferred implementation, the crystal metal component has hydroxyapatite structure.
In another embodiment, the present invention is a kind of method for preparing carbon monoxide-olefin polymeric of the present invention, and this method comprises:
A) make the mixture of the reactive sources material that contains alkalinous metal B, nonessential Ni, D skeleton component and nonessential alkali metal A, be enough to form at pH value 8-14, temperature and time under the condition of crystal metal oxide component and react, the mixture that contains composition can be represented by following formula:
hA 2O:jBO t/2:kNiO:D 2O 5:lN:mH 2O
Wherein N is that a kind of mineralizer, " h " size are 40-500 for 0-1.0, " l " size for 0-20, " m " size for 0.10-6.0, " k " size for 0-10, " j " size;
B) when " k " is 0, the crystal metal oxide component is contacted with the nickel salt aqueous solution that is selected from nickel nitrate, nickel chloride, nickelous bromide, nickel acetate and composition thereof; With
C) with step (a) or crystal metal oxide component (b) 600 ℃-1000 ℃ temperature lower calcination 1-10 hour to make catalyst.
Another embodiment of the present invention is a kind of in the presence of carbon monoxide-olefin polymeric of the present invention, makes the method for light hydrocarbon and oxidant prepared in reaction synthesis gas under reaction condition.
The accompanying drawing summary
Accompanying drawing has compared the amount of coke for the dead catalyst of catalyst of the present invention and conventional catalyst.
Detailed Description Of The Invention
Carbon monoxide-olefin polymeric of the present invention has comprised foregoing component. Usually metal B has sizable cation radius, is generally 0.85 -1.40 , cationic electric charge be+2 or+3. These metals extensively are present in alkaline-earth metal, the rare earth metal, in some cases, have simultaneously transition metal, for example Cd2+And Hg2+, and main group metal, for example Pb2+In. Preferred situation is that B is selected from Ca2+、Sr 2+、Cd 2+、Pb 2+、Ba 2+、La 3+、Eu 3+、Gd 3+、Pr 3+、Nd 3+、Sm 3+、 Y 3+、Yb 3+And composition thereof. When B was the mixture of Sr and the another kind of metal that is selected from alkalinous metal, catalyst showed extraordinary result. B is preferably and comprises Sr and be selected from Ca2+、Ba 2+、La 3+、 Eu 3+、Gd 3+、Pr 3+、Nd 3+、Sm 3+、Y 3+、Yb 3+And composition thereof bimetallic mixture.
When B only was a kind of metal, its weighted average chemical valence was the chemical valence of this metal. When using more than a kind of alkalinous metal, total amount is provided by following formula:
B w t + = B i t i + + B j t j + + B k t k + + · · ·
And its weighted average chemical valence " t " is provided by following formula:
t = t i · i + t j · j + t k · k + · · · w
The weighted average chemical valence of anion (" u ") comes in a similar manner to determine, and depends on existing CO in the composition3 2-Amount and oxidation state be-1 G other may between relativeness. If therefore total amount or " y " of G are decided by formula y=p+q, wherein " p " is CO3 2-Mol ratio, " q " is that chemical valence is the mol ratio of-a kind, then average valence is
u = - 2 p - q p + q
Come the crystal metal oxide component of Kaolinite Preparation of Catalyst by the source material that in the first solution, dissolves Ni (if having mixed in the skeleton) and alkalinous metal. Dissolving skeleton component and nonessential alkali metal source material in the second solution. Two kinds of solution and any nonessential mineralizer are fully mixed to form reactant mixture. The pH value of reactant mixture is generally 8.0-14.0, and controls by adding alkali metal hydroxide in the reactant mixture or the amount of mineralizer to. Fully after the homogenizing, reactant mixture was cleared up 2 hours to 7 days under 20 ℃-200 ℃ temperature, preferably cleared up 12-96 hour 50 ℃ of-150 ℃ of lower hydro-thermals, more preferably cleared up 24-48 hour 75 ℃ of-125 ℃ of lower hydro-thermals. After clearing up, product is by filtration or centrifugation, with deionized water washing, at room temperature dry or lower dry at 200 ℃ in baking oven. Desciccate is subsequently in air stream, in 600 ℃-1000 ℃ lower calcinings 1-10 hour. Drying can also not necessarily be sieved afterwards or be adjusted the sample particle diameter.
Usually after initial Hydrothermal Synthesis, testing as can be known by the x x ray diffraction, the crystal metal oxide component has hydroxyapatite structure. Although be not regularly, occasionally, the product of Hydrothermal Synthesis also can comprise some Ni (OH)2 Isolated hydroxyapatite from Hydrothermal Synthesis calcined to cause in the final catalyst producing a plurality of phases (this depends on the condition of calcining). Except hydroxyapatite, also can produce some NiO in the skeleton outside, or produce other phase, such as Sr3(PO 4) 2 In some cases, calcining can form new structure (for example SrCaP-1 among the embodiment 8). Therefore the crystal metal component can contain the polycrystal phase.
In the process that forms above-mentioned reactant mixture, the alkali metal source material can include, but are not limited to hydroxide, acetate, halide or the carbonate of sodium, potassium, lithium, rubidium or caesium. Alkalinous metal source material can comprise nitrate, chloride and the acetate of calcium, strontium, lead, cadmium, barium, lanthanum, neodymium, gadolinium, europium, yttrium, ytterbium and samarium. Nickel source material comprises nickel nitrate, nickel chloride and nickel acetate. Mineralizer such as hydroxide, fluoride, chloride or carbonate for example form of alkali metal salt, organic ammonium salt is introduced, described alkali metal salt is sodium fluoride or sodium carbonate for example, described organic ammonium salt is TMAH or tetraethyl ammonium fluoride for example, perhaps under halid situation, introduce with the form of the acid of for example HF or HCl. P in the skeleton and V pass through such as phosphoric acid, Na2HPO 4，、Na 3PO 4、Na 3VO 4，、 KVO 3And V2O 5And so on the source material introduce in the reactant mixture.
Generally, the composition of reactant mixture can represent by following formula:
             hA 2O:jBO t/2:kNiO:D 2O 5:lN:mH 2O
Wherein N is that a kind of mineralizer, " h " size are 40-500 for 0-1.0, " l " size for 0-20, " m " size for 0.10-6.0, " k " size for 0-10, " j " size. When " k " is 0, before calcining, nickel is dispersed on the crystal metal oxide component (not containing nickel in its crystalline framework).
The structure of crystal metal oxide component of the present invention is determined by the x ray analysis.By adopting standard x ray powder diffraction technology can obtain x ray diagram in following examples.Radiation source is the x ray tube of the high brightness operated under 45kV and 35ma.Obtain by suitable computer based technology from the alpha-emitting diffraction pattern of copper K-.With powdered sample 2 ° to 70 ° (2 θ) between the continuous sweep of 2 ° of per minutes (2 θ) to dull and stereotyped compacting.The interplanar distance (d) that in the dust is unit can obtain from the position of the diffraction maximum represented with θ, and wherein θ is the Bragg angle that observes from digitalized data.The integral area of the diffraction maximum of intensity after by subtracting background is determined " I 0" be the intensity at the strongest line or peak, " I " is the intensity at other each peak.
Perhaps (be derived from Siemens Corporation by the x-radiographic source that utilizes Siemens D-500 x-ray powder diffraction instrument, Siemens K-805 type, Cherry Hill, N.J.) and the computer based technology of suitable computer interface can obtain from the alpha-emitting x-ray of copper K-pattern.
Parameter 2 θ define human error and machine error, and both combinations all can produce ± 0.4 ° deviation for 2 θ values of each report.Certainly this deviation also shows the report value of the d-spacing that calculates from 2 θ values.Such inexactness spreads all over this field, but is not sufficient to hinder the differentiation between this crystalline material and other composition.In some x-ray patterns of being reported, the relative intensity of d-spacing is represented by representing very strong, strong, medium and weak symbol vs, s, m and w respectively.With 100 * I/I oMeter, more than expression may be defined as:
W=0-15; M=15-60; S=60-80 and vs=80-100.
In some cases, the purity of synthetic product can be estimated with reference to its X-ray diffraction pattern.Therefore, for example,, then only mean the line that the X-ray diffraction pattern of sample is not produced by crystalline impurities, but do not mean that and do not have amorphous substance if claim that sample is pure.
For ease of reference, different types of structure in following examples has been provided name as CaSrNiP-1 artificially.Therefore CaSrNiP-1 has identical structure with KCaSrNiP-1, that is: 1 type structure.Element in the name has been represented composition.A kind of specific structure is a hydroxyapatite structure, is expressed as-HA.Crystal metal oxide component used in the catalyst of the present invention is preferably apatite and hydroxyapatite structure.These structures further define, can be with reference to Kikuchi, and Masanori; Yamazaki, Atsushi; Otsuka, Ryohei; Akao, Masaru; Aoki, the crystal structure of the hydroxyapatite that the Sr that Hideki is synthesized by hydro-thermal method replaces, J.Solid State Chem. (1994), 113 (2), the atom site of being put down in writing among the 373-8.
Based on the concrete application of catalyst expection of the present invention, mixing nickel in crystal metal oxide skeleton does not need further processing that enough activity can be provided.Synthesize in the process of the crystal metal oxide that does not have skeleton nickel, because the cause of catalytic activity needs to add nickel component (for example Ni or NiO).The crystal metal oxide component of nickel has also been mixed in hope in skeleton surface is dispersed with the nickel component.Any step of nickel of disperseing on the crystal metal oxide component was all carried out before calcining step
If desired, the nickel component can adopt and can make it homodisperse any-mode and deposit on the crystal metal oxide.Usually the crystal metal oxide component is contacted (as dipping) with the aqueous solution that is selected from nickel salts such as nickel nitrate, nickel chloride, nickelous bromide, nickel acetate with the nickel deposited component.As the nickel component of dispersion that reaches required load capacity is desired, can by as usual manners such as dipping, spraying under desired contact conditions (for example time, temperature and solution concentration), contact.
The method for optimizing of nickel component deposition is to use the rotary drier of carrying vapour chuck to realize the evaporation dipping.The particle of crystal metal oxide component immerses in the maceration extract of any foregoing salting liquid formation, wherein contains the slurries and the nickel solution of metal oxide component in drier.The rotation of drier is rotated crystal metal oxide component wherein, the evaporation of the maceration extract that contacts with the crystal metal oxide of described rotation that added steam promotion in the drier chuck.
After dipping was finished, the nickeliferous crystal metal oxide particle of gained descended dry 1-48 hour at 20 ℃-250 ℃.Existing nickel component disperses the crystal metal oxide on it to calcine according to above-mentioned technology subsequently.No matter the deposition form of nickel component how, calcining can be converted into nickel oxide basically with it usually.
Except the catalyst activity component, other metal, co-catalyst agent metal for example, also can be when contacting with nickel solution with above-mentioned crystal metal oxide component essentially identical step, simultaneously or be deposited on successively on the crystal metal oxide component.Be used for improving active and/or optionally promoter metal comprise lanthanum and cerium.
Catalyst of the present invention can be used in the foregoing synthesis gas process.These technologies are included in condition for validity and the crystal metal oxide catalyst exists down, and light hydrocarbon is contacted with oxidant.The preferred C of light hydrocarbon 1-C 4Alkane, namely for methane, ethane, propane and butane.Natural gas, the impure mixture of a kind of methane and other component also is a kind of preferred raw material.Also can use alkene and other unsaturated hydrocarbons, but they generate polymer and other undesirable accessory substance easily.Preferred oxidant is an oxygen when being used for partial oxidation, and when being used for steam reformation, preferred oxidant is a steam.Pure oxygen be can also mix in the reactant mixture, but air or enrichment air more commonly mixed.At CO 2In the reformation carbon dioxide also is well known as oxidant.
Crystal metal oxide catalyst of the present invention has improved partial oxidation, steam reformation, self-heating recapitalization and CO 2Reforming method.The operating condition that these process using are known: temperature is generally 600 ℃-1200 ℃, and absolute pressure is the 5-60 atmospheric pressure, and gas hourly space velocity (GHSV) is 500-500000hr -1GHSV equals the gas volume hour flow velocity of all raw material components divided by the beds volume.
When catalyst of the present invention was used for foregoing any technology, the characteristics of this catalyst were to reduce the trend that coke forms.It is believed that mixing nickel in the skeleton structure of crystal metal oxide can give its certain decentralization, this was not known in the prior art.The catalyst metals of conventional surface impregnation, though disperse at first fine, under the condition of reorganization of harshness, also migration and reuniting easily.The metal site of the reunion that is caused can be caused fibrous and growth stratiform carbon.On the contrary, by attempting in initial synthetic process, evenly mix nickel in catalyst backbone of the present invention, high initial decentralization and strong interaction it is believed that migration and extensive reunion that has prevented nickel, and the migration of nickel and the characteristics of conventional catalyst just of reuniting on a large scale.In a word, catalyst of the present invention has been eliminated the nucleation site of carbon growth basically.
Catalyst of the present invention has alleviated excessive oxygen and steam has been injected to suppress the demand of partial oxidation and reforming reaction coking.Excess of oxygen or steam mean and have surpassed the stoichiometric number of reacting required, have perhaps surpassed the desirable value that best synthesis gas is formed, the dilution steam generation that is used to suppress the catalyst coking that for example adds in partial oxidation.
For partial oxidation, atomic carbon is closely related to the atomic ratio of oxygen (C: O than) in the coking of catalyst and the reactant mixture under condition of similarity.Conventional catalyst is usually at C: O (is CH than greater than 0.5 4: O 2Ratio is greater than 1) time, show tangible coking rate.On the contrary, catalyst of the present invention than under the 0.5-2.0, generates minimum coking at preferred C: O in partial oxidation technology.Catalyst of the present invention provides the coke of reduction to form in the trend in the dry type partial oxidation technology, and it reduces as the ability of the charge velocity of the steam of coke formation inhibitor also favourable to steam reformation.Usually by C: H 2The coke that O ratio or carbon are recently weighed catalyst in the steam reformation to the mole of steam forms trend.When adopting steam reforming catalyst, carbon/steam mol ratio can be equal to or greater than 2.0.Advantage may be embodied in the catalyst life of length, and/or reduces communal facility (as compression) expense, thermic load, and the consumption of raw materials due to more critical conditions (as higher C: O ratio) is operated down.
Following examples illustrated the catalyst of some kind of the present invention.
Embodiment
Embodiment 1
Preparation Na-Ni-Sr-P-O
Phosphoric acid (H with 159g 85% 3PO 4) add the 200g deionized water that is arranged in glass beaker to.Similar ground, dissolving 220.8g NaOH in the 300g deionized water.Two kinds of solution are all placed ice bath.By dissolving 131.4g Sr (NO in 331.4 deionized waters 3) 2And 20.0gNi (NO 3) 26H 2O prepares the third solution.Freezing NaOH solution slowly stirs and adds H to 3PO 4In the solution, the mixture of gained moves to 2 liters plastic beaker, and places under the high speed agitator.In phosphate solution, add Sr/Ni solution, acutely mix simultaneously, formed gelatinous precipitate.With reactant mixture homogenizing 1 hour, move in 21 liter the polytetrafluoroethylene (PTFE) bottle, under self-generated pressure, cleared up 4 days at 100 ℃.By filtering to isolate solid product, with deionized water fully wash, dry under the room temperature, subsequently 800 ℃ of calcinings 1.5 hours.
Elementary analysis shows that the empirical formula of catalyst is Na 0.15Ni 0.17Sr 1.55PO 4.295, X-ray diffraction shows that also catalyst has hydroxyapatite structure simultaneously, but does not almost record NiO.The characteristic curve of catalyst provides in table 1 in the X-ray diffraction pattern.This material is called as SrP-HA.
Table 1
2-θ d() I/I o％ Phase
10.46 8.45 w SrP-HA
21.02 4.22 w SrP-HA
21.94 4.05 w SrP-HA
24.46 3.64 w SrP-HA
26.68 3.34 w-m SrP-HA
27.92 3.19 w-m SrP-HA
30.62 2.92 vs SrP-HA
31.76 2.82 m SrP-HA
32.50 2.75 w SrP-HA
37.34 2.41 w NiO
38.38 2.34 w SrP-HA
40.46 2.23 w SrP-HA
41.56 2.17 w SrP-HA
43.36 2.09 w NiO
44.70 2.03 m SrP-HA
46.04 1.97 w SrP-HA
47.00 1.93 m SrP-HA
48.56 1.87 w SrP-HA
49.38 1.84 w SrP-HA
49.90 1.83 m SrP-HA
Embodiment 2
Preparation Na-Ni-Ca-P-O
Phosphoric acid (H with 56.25g 85% 3PO 4) add the 150g deionized water that is arranged in glass beaker to.Similar ground, dissolving 156g NaOH in the 180g deionized water.Two kinds of solution are all placed ice bath.By dissolving 103.5g Ca (NO in 110 deionized waters 3) 24H 2O and 14.0gNi (NO 3) 26H 2O prepares a kind of solution.Add slow stirring of freezing NaOH solution to H 3PO 4In the solution, the mixture of gained moves to 2 liters plastic beaker, and places under the high speed agitator.In phosphoric acid solution, add Ca/Ni solution, acutely mix simultaneously, formed gelatinous precipitate.With reactant mixture homogenizing 1 hour, move to 21 liter polytetrafluoroethylene (PTFE) bottle, under self-generated pressure, cleared up 4 days at 100 ℃.By filtering to isolate solid product, with deionized water fully wash, dry under the room temperature, subsequently 800 ℃ of calcinings 1.5 hours.
What elementary analysis showed catalyst is Na based on anhydrous empirical formula 0.15Ni 0.17Ca 1.60PO 4.345, the X-ray diffraction pattern shows that also catalyst has hydroxyapatite structure simultaneously, contains minor N iO impurity.The characteristic curve of catalyst provides in table 2 in the X-ray diffraction pattern.
Table 2
2-θ d() I/I o％ Phase
10.80 8.19 w CaP-HA
16.80 5.27 w CaP-HA
18.77 4.72 w CaP-HA
21.72 4.09 w CaP-HA
22.84 3.89 w CaP-HA
25.84 3.45 m CaP-HA
28.08 3.18 w CaP-HA
28.90 3.09 w-m CaP-HA
31.74 2.82 vs CaP-HA
32.16 2.78 s-vs CaP-HA
32.88 2.72 m-s CaP-HA
34.02 2.63 m CaP-HA
35.44 2.53 w CaP-HA
37.20 2.41 w-m NiO
39.18 2.30 w CaP-HA
39.76 2.27 m CaP-HA
41.96 2.15 w CaP-HA
43.24 2.09 m NiO
43.84 2.06 w CaP-HA
46.66 1.94 m CaP-HA
48.08 1.89 w CaP-HA
49.44 1.84 m CaP-HA
50.46 1.81 w-m CaP-HA
51.24 1.78 w CaP-HA
52.06 1.76 w CaP-HA
53.16 1.72 w-m CaP-HA
Embodiment 3
The Na-Ca-P-O of preparation dipping Ni
Take by weighing the 627g deionized water.Part water is used for diluting the phosphoric acid (H of 160g 85% 3PO 4), part water is used for dissolving 223g NaOH.Place ice bath freezing these solution.The remaining water-soluble 164.36g Ca (NO that separates 3) 24H 2O.With the freezing freezing H of sodium hydroxide solution stirring adding to 3PO 4In the solution, and the mixture of gained placed under the high speed agitator stir.In sodium radio-phosphate,P-32 solution, add calcium nitrate solution, acutely mix simultaneously, in preparation process, formed gel.After the interpolation, with reactant mixture homogenizing 20 minutes again.Reactant mixture moves to 1 polytetrafluoroethylene (PTFE) bottle subsequently, clears up 72 hours at 100 ℃ under self-generated pressure.By filtering to isolate solid product, spend drying under deionised water, the room temperature, X-ray diffraction shows the hydroxyapatite structure with calcium phosphate solid.
By dissolving 20.32g Ni (NO in 200g water 3) 26H 2O prepares solution.The calcium phosphate solid of 74g adds in the nickel solution, and uses agitator to make slurries.Slurries are added in the rotary evaporator of carrying vapour chuck, rotating provided steam to be dried until solid in evaporimeter after 15 minutes.The solid of the dipping Ni of gained is 150 ℃ of following dried overnight in baking oven, subsequently 800 ℃ of calcinings 1.5 hours.
What elementary analysis showed solid is Na based on anhydrous empirical formula 0.18Ni 0.16Ca 1.55PO 4.13The characteristic curve of catalyst provides in table 3 in the X-ray diffraction pattern.
Table 3
2-θ d() I/I o％ Phase
10.74 8.23 w CaP-HA
16.74 5.29 w CaP-HA
21.69 4.09 w CaP-HA
22.81 3.89 w CaP-HA
25.80 3.45 m CaP-HA
28.04 3.18 w CaP-HA
28.86 3.09 w CaP-HA
31.70 2.82 vs CaP-HA
32.12 2.78 m CaP-HA
32.84 2.73 s CaP-HA
33.62 2.66 w CaP-HA
34.00 2.64 m CaP-HA
35.40 2.53 w CaP-HA
37.18 2.42 w NiO
39.14 2.30 w CaP-HA
39.74 2.27 m CaP-HA
40.93 2.20 w CaP-HA
41.94 2.15 w CaP-HA
43.23 2.09 m NiO
43.78 2.07 w CaP-HA
46.62 1.95 m CaP-HA
48.04 1.89 w CaP-HA
49.42 1.84 m CaP-HA
50.44 1.81 w CaP-HA
51.22 1.78 w CaP-HA
52.02 1.76 w CaP-HA
53.10 1.72 w CaP-HA
Embodiment 4
The Na-Sr-P-O of preparation dipping Ni
Phosphoric acid (H with 200g deionized water dilution 155.6g 85% 3PO 4).With 250g deionized water dissolving 216g NaOH with the preparation sodium hydroxide solution.In that two kinds of solution are made it freezing with ice bath earlier before the mixed preparation sodium radio-phosphate,P-32 solution, sodium radio-phosphate,P-32 solution is placed in the polytetrafluoroethylene beaker, and places under the high speed agitator and stir.With 279g deionized water dissolving 142.85g Sr (NO 3) 2Prepare another kind of solution, it is added in the sodium radio-phosphate,P-32 solution, vigorous stirring is to form gel simultaneously.Add the 250g deionized water and reduce its denseness in mixture, described mixture is moved to 21 liter polytetrafluoroethylene (PTFE) bottle subsequently by homogenizing 1 hour, clears up 2 days at 100 ℃ under self-generated pressure.By filtering to isolate solid product, spend under deionised water, the room temperature dry.X-ray diffraction shows the strontium phosphate product with hydroxyapatite structure.
Dissolving 19.98g Ni (NO in 200g water 3) 26H 2O prepares nickel nitrate solution, by 111g strontium phosphate solid is added in this solution, and it is stirred to make slurries.Rotate slurries in the rotary evaporator of carrying vapour chuck, rotating provided steam to be dried until solid after 15 minutes.The solid of the dipping Ni of gained is 150 ℃ of following dried overnight in baking oven, subsequently 800 ℃ of calcinings 1.5 hours.
What elementary analysis showed solid is Na based on anhydrous empirical formula 0.17Ni 0.17Sr 1.54PO 4.295X-ray diffraction the analysis showed that catalyst is made of hydroxyapatite and NiO component.The characteristic curve of catalyst provides in table 4 in the X-ray diffraction pattern.
Table 4
2-θ d() I/I o％ Phase
10.38 8.51 W SrP-HA
20.93 4.24 W SrP-HA
21.86 4.06 W SrP-HA
24.38 3.65 W SrP-HA
26.60 3.35 W SrP-HA
27.84 3.20 w-m SrP-HA
30.48 2.93 vs SrP-HA
31.66 2.82 M SrP-HA
32.38 2.76 W SrP-HA
32.74 2.73 W SrP-HA
37.18 2.42 W NiO
38.30 2.35 W SrP-HA
40.40 2.23 W SrP-HA
41.48 2.18 W SrP-HA
42.85 2.11 W SrP-HA
43.24 2.09 W NiO
44.62 2.03 w-m SrP-HA
45.96 1.97 W SrP-HA
46.94 1.93 M SrP-HA
48.48 1.88 W SrP-HA
49.30 1.85 W SrP-HA
49.80 1.83 W SrP-HA
50.05 1.82 W SrP-HA
Embodiment 5
Preparation Cs-Na-Sr-Ca-P-O crystal metal oxide
With 148g deionized water dissolving 21.44g Na 2HPO 47H 2O makes the solution that adds 31.93g CsOH (50%).Mixture is placed on mixing under the heidolph blender.Utilize 25.0g deionized water dissolving 7.5g Sr (NO respectively 3) 2, 8.37g Ca (NO 3) 24H 2O and 2.29g Ni (NO 3) 26H 2O acutely mixes with phosphoric acid solution to form metal-nitrate solutions simultaneously.The mixture retrogradation of gained, but reduce by further stirring viscosity.Continue homogenizing 2 hours.Reactant mixture moves to 1 polytetrafluoroethylene (PTFE) bottle, clears up 48 hours at 100 ℃ under self-generated pressure.By filtering to isolate solid product, with deionized water fully wash, dry under the room temperature.Before the test solid of drying was calcined 5 hours at 800 ℃.
What elementary analysis showed solid after the gained calcining is Cs based on anhydrous empirical formula 0.002Na 0.164Ni 0.076Sr 0.755Ca 0.757PO 4.253X-ray diffraction shows that catalyst is the mixture that hydroxyapatite and minor N iO component constitute, and described hydroxyapatite is called CaSrP-HA, is a small amount of novel substance component that is called SrCaP-1 of preparation among the embodiment 8.The characteristic curve of crystal metal oxide provides in table 5 in the X-ray diffraction pattern.
Table 5
2-θ d() I/I o％ Phase
10.66 8.29 w CaSrP-HA
13.29 6.65 w SrCaP-1
16.62 5.33 w SrCaP-1
21.42 4.14 w CaSrP-HA
25.18 3.53 w-m CaSrP-HA
25.90 3.44 w SrCaP-1
27.40 3.25 w CaSrP-HA
28.46 3.13 w CaSrP-HA
29.01 3.08 w SrCaP-1
30.19 2.96 w SrCaP-1
31.18 2.87 s CaSrP-HA
31.44 2.84 vs CaSrP-HA
32.34 2.77 m CaSrP-HA
33.26 2.69 w SrCaP-1
33.58 2.67 w SrCaP-1
34.65 2.59 w CaSrP-HA
37.34 2.41 w NiO
39.14 2.30 w CaSrP-HA
40.62 2.22 w CaSrP-HA
41.19 2.19 w CaSrP-HA
42.72 2.11 w CaSrP-HA
43.50 2.08 w CaSrP-HA
45.72 1.98 w-m CaSrP-HA
47.12 1.93 w CaSrP-HA
48.22 1.89 m CaSrP-HA
49.52 1.84 w CaSrP-HA
50.30 1.81 w CaSrP-HA
50.98 1.79 w CaSrP-HA
51.64 1.77 w CaSrP-HA
Embodiment 6
Preparation Na-Ni-La-Sr-P-O
Dilute the H of 46.12g respectively with the 300g deionized water 3PO 4(98%) with 300g deionized water dissolving 65.95g NaOH., carefully mix subsequently freezing 1 hour of two kinds of solution with ice.Utilize the water-soluble 7.50g of the separating Ni of 300g (NO respectively 3) 26H 2O, 31.8g Sr (NO 3) 2With 21.6g La (NO 3) 3To form metal-nitrate solutions.In super mixer, in phosphate solution, add the 300g deionized water.Stir the adding nitrate solution in phosphate solution, homogenizing 1 hour moves to 1 polytetrafluoroethylene (PTFE) bottle with it, clears up 48 hours at 100 ℃ under self-generated pressure.By filtering to isolate solid product, with deionized water fully wash, dry under the room temperature, before test earlier 800 ℃ of calcinings 5 hours.
What elementary analysis showed solid after the gained calcining is Na based on anhydrous empirical formula 0.199Ni 0.064La 0.333Sr 0.995PO 4.162X-ray diffraction shows also that to the analysis of catalyst key component has hydroxyapatite structure (being called LaSrP-HA) and Sr 3(PO 4) 2Almost detect in the diffraction pattern less than NiO.The characteristic curve of catalyst provides in table 6 in the X-ray diffraction pattern.
Table 6
2-θ d() I/I o％ Phase
19.57 4.53 w Sr 3(PO 4) 2
21.06 4.22 w LaSr-HA
22.07 4.03 w LaSr-HA
24.64 3.61 w LaSr-HA
26.24 3.39 w Sr 3(PO 4) 2
26.84 3.32 w LaSr-HA
28.00 3.18 w LaSr-HA
29.58 3.02 vs Sr 3(PO 4) 2
30.64 2.92 vs LaSr-HA
31.80 2.81 w-m LaSr-HA
33.34 2.69 s LaSr-HA
36.12 2.49 w Sr 3(PO 4) 2
37.04 2.42 w Sr 3(PO 4) 2
38.50 2.34 w Sr 3(PO 4) 2
39.00 2.31 w LaSr-HA
39.84 2.26 w Sr 3(PO 4) 2
40.94 2.20 w Sr 3(PO 4) 2
41.86 2.16 w Sr 3(PO 4) 2
42.98 2.10 m LaSr-HA
43.42 2.08 m Sr 3(PO 4) 2
44.88 2.02 m Sr 3(PO 4) 2
45.18 2.01 m LaSr-HA
46.20 1.96 w Sr 3(PO 4) 2
47.28 1.92 m LaSr-HA
48.74 1.87 w LaSr-HA
49.62 1.84 w-m LaSr-HA
49.98 1.82 m Sr 3(PO 4) 2
Embodiment 7
Preparation Na-Sr-Ni-P-O
Phosphoric acid (85%) with 220g deionized water dilution 57.65g.Similar ground, dissolving 82.50g NaOH in the 220g deionized water.Make two kinds of solution in ice bath freezing 1 hour.By dissolving 14.54g Ni (NO in the 100g deionized water 3) 26H 2O and 14.3g Sr (NO 3) 2Prepare a kind of metal-nitrate solutions.Under super mixer, in NaOH solution, carefully add phosphate solution.Add metal-nitrate solutions subsequently, and made it homogenizing 1 hour, then it is moved to 1 polytetrafluoroethylene (PTFE) bottle, under self-generated pressure, cleared up 48 hours at 100 ℃.By filtering to isolate solid product, with deionized water fully wash, dry under the room temperature.Dry solid was calcined 5 hours at 800 ℃ earlier before test.
What elementary analysis showed solid after the gained calcining is Na based on anhydrous empirical formula 0.105Sr 1.52Ni 0.35PO 4.423X-ray diffraction has hydroxyapatite structure to its main catalytic component that the analysis showed that of catalyst.Also detected Sr simultaneously 3(PO 4) 2And NiO.The characteristic curve of catalyst provides in table 7 in the X-ray diffraction pattern.
Table 7
2-θ d() I/I o％ Phase
10.39 8.51 w SrP-HA
19.48 4.55 w Sr 3(PO 4) 2
20.94 4.24 w SrP-HA
21.86 4.06 w SrP-HA
24.38 3.65 w SrP-HA
26.19 3.40 w Sr 3(PO 4) 2
26.60 3.35 w-m SrP-HA
27.84 3.20 w-m Sr 3(PO 4) 2
29.52 3.02 m SrP-HA
30.50 2.93 vs SrP-HA
31.68 2.82 m SrP-HA
32.38 2.76 w SrP-HA
33.16 2.70 m Sr 3(PO 4) 2
37.18 2.42 w NiO
38.30 2.35 w SrP-HA
39.61 2.27 w Sr 3(PO 4) 2
40.36 2.23 w SrP-HA
40.98 2.20 w Sr 3(PO 4) 2
41.46 2.18 w SrP-HA
42.72 2.11 w Sr 3(PO 4) 2
43.24 2.09 w NiO
44.62 2.03 m SrP-HA
45.00 2.01 w Sr 3(PO 4) 2
45.96 1.97 w SrP-HA
46.92 1.93 m SrP-HA
48.47 1.88 m SrP-HA
49.30 1.85 m SrP-HA
49.83 1.83 s SrP-HA
Embodiment 8
Preparation Na-Ni-Ca-Sr-P-O
Make adding 88.67gNa with 602g deionized water dissolving 13.74g NaOH bead 2HPO 47H 2The solution of O.By in the 100.0g deionized water, dissolving 35.0gSr (NO respectively 3) 2, 39.06g Ca (NO 3) 24H 2O and 10.69g Ni (NO 3) 26H 2O prepares a kind of metal-nitrate solutions, under violent the mixing it is sneaked into phosphate solution.Made the reactant mixture homogenizing 1 hour, and then it was moved to 1 polytetrafluoroethylene (PTFE) bottle, under self-generated pressure, cleared up 48 hours at 95 ℃.By filtering to isolate solid product, with deionized water fully wash, dry under the room temperature.Dry solid was calcined 5 hours at 800 ℃ earlier before test.
What elementary analysis showed solid after the gained calcining is Na based on anhydrous empirical formula 0.12Ni 0.14Ca 0.71Sr 0.71PO 4.12The X-ray diffraction data show and contain a kind of new structure in the catalyst, are called SrCaP-1 at this, it is characterized in that the hexagonal crystal system structure cell of lattice parameter a=10.614 , c=19.147 .The characteristic curve of catalyst provides in table 8 in the X-ray diffraction pattern.In this pattern, also can detect small amount of N iO.
Table 8
2-θ d() I/I o％ Phase
10.68 8.28 w SrCaP-1
13.32 6.64 w SrCaP-1
13.88 6.38 w SrCaP-1
16.68 5.31 m SrCaP-1
20.91 4.25 w SrCaP-1
21.44 4.14 w SrCaP-1
25.19 3.53 m SrCaP-1
26.06 3.42 w-m SrCaP-1
26.87 3.32 w SrCaP-1
27.30 3.26 m SrCaP-1
29.12 3.06 m SrCaP-1
30.36 2.94 vs SrCaP-1
31.80 2.81 m SrCaP-1
32.35 2.77 w SrCaP-1
33.76 2.65 s SrCaP-1
34.82 2.57 w SrCaP-1
36.66 2.45 w SrCaP-1
37.22 2.41 w NiO
38.81 2.32 w SrCaP-1
40.34 2.23 w SrCaP-1
40.82 2.21 w SrCaP-1
42.01 2.15 w SrCaP-1
42.50 2.13 w SrCaP-1
43.20 2.09 w NiO
43.68 2.07 w-m SrCaP-1
43.94 2.06 w SrCaP-1
44.36 2.04 w SrCaP-1
46.00 1.97 m SrCaP-1
47.04 1.93 m SrCaP-1
47.46 1.91 w SrCaP-1
48.52 1.87 w SrCaP-1
49.31 1.85 w SrCaP-1
49.78 1.83 w SrCaP-1
Embodiment 9
Preparation Na-Ni-Ca-P-O
With the phosphoric acid (85%) of 140g deionized water dilution 230.6g, and with 1860g deionized water dissolving 330.0g NaOH bead.Careful mix two kinds of solution and under violent condition of mixing, before wherein adding the 1500g deionized water, make it all freezing with ice bath earlier again.The slurries of gained move in one 5 liters the flask and are heated to 35 ℃ of fully dissolvings.In the 500g deionized water, dissolve 236.15gCa (NO respectively 3) 24H 2O and 32.31g Ni (NO 3) 26H 2O.In about 2 minutes time, metal-nitrate solutions is added in the slurries that dissolved.Flask is equipped with temperature controller, condenser and mechanical agitator.Reactant mixture heated 60 hours down at 100 ℃.By filtering to isolate solid product, with deionized water fully wash, at room temperature dry, subsequently before test earlier 800 ℃ of calcinings 5 hours.
What elementary analysis showed solid after the gained calcining is Na based on anhydrous empirical formula 0.1122Ni 0.175Ca 1.64PO 4.37X-ray diffraction shows that catalyst has hydroxyapatite structure, is called CaP-HA.Also detected minor N iO simultaneously.The characteristic curve of catalyst provides in table 9 in the X-ray diffraction pattern.
Table 9
2-θ d() I/I o％ Phase
10.80 8.19 W CaP-HA
16.82 5.27 W CaP-HA
21.72 4.09 W CaP-HA
22.78 3.90 W CaP-HA
25.80 3.45 M CaP-HA
28.06 3.18 W CaP-HA
28.90 3.09 W CaP-HA
31.72 2.82 VS CaP-HA
32.12 2.78 S CaP-HA
32.88 2.72 M CaP-HA
33.98 2.64 M CaP-HA
35.46 2.53 W CaP-HA
37.29 2.41 W NiO
39.28 2.29 W CaP-HA
39.80 2.26 w-m CaP-HA
42.04 2.15 W CaP-HA
43.13 2.10 W NiO
43.74 2.07 W CaP-HA
46.68 1.94 M CaP-HA
48.06 1.89 W CaP-HA
49.40 1.84 M CaP-HA
Embodiment 10
Preparation Na-Ni-Sr-P-O
With 1000g deionized water dissolving 330.0g NaOH bead.It is freezing with ice bath that this solution moves in one 5 liters the flask back.In this flask, add the phosphoric acid (85%) (using the 400.0g deionized water) of 400g, also add other 1000g water its dilution and stirring.Be heated to 50 ℃ of suspension dissolvings that make gained.By dissolving 211.63g Sr (NO in the 600g deionized water 3) 2And 32.31gNi (NO 3) 26H 2O prepares metal-nitrate solutions, and it is joined in the flask while stirring.Flask is equipped with condenser and temperature controller.By vigorous stirring, reactant mixture was cleared up under 100 ℃ 60 hours.By filtering to isolate solid product, spend under deionised water, the room temperature dry.Dry solid was calcined 5 hours at 800 ℃ earlier before test.
What elementary analysis showed solid after the gained calcining is Na based on anhydrous empirical formula 0.098Ni 0.169Sr 1.518PO 4.236X-ray diffraction shows that catalyst is by being called SrNiP-HA, having the single-phase of hydroxyapatite structure and constitute.The characteristic curve of catalyst provides in table 10 in the X-ray diffraction pattern.
Table 10
2-θ d() I/I o％ Phase
10.44 8.47 w SrNiP-HA
21.04 4.22 w SrNiP-HA
21.92 4.06 w SrNiP-HA
24.46 3.64 w SrNiP-HA
26.70 3.34 w-m SrNiP-HA
27.92 3.19 w-m SrNiP-HA
30.60 2.92 vs SrNiP-HA
31.78 2.81 m SrNiP-HA
32.46 2.76 w SrNiP-HA
38.38 2.34 w SrNiP-HA
40.42 2.23 w SrNiP-HA
41.54 2.17 w SrNiP-HA
42.90 2.11 w SrNiP-HA
44.68 2.03 m SrNiP-HA
46.04 1.97 w SrNiP-HA
47.04 1.93 m SrNiP-HA
48.60 1.87 w SrNiP-HA
49.36 1.84 w SrNiP-HA
50.02 1.82 m SrNiP-HA
Embodiment 11
Catalyst coking research
Test in the methane portion oxidation environment has shown that the STRENGTH ON COKE mutually of the embodiment of the invention 1,2,4,6 and 8 described carbon monoxide-olefin polymerics forms trend.The conventional partial oxidation catalyst (embodiment 17) that the coke of above-mentioned catalyst is formed speed, conversion ratio and selectivity and the conventional partial oxidation catalyst that contains the nickel that loads on the alumina support (embodiment 16) and also contain the magnesia co-catalyst is compared.
Loaded the catalyst samples of 2.4g in the test technology, sieved into earlier 40-60 purpose particle diameter, in the quartz reactor of packing into then.Reactor is under the situation that purges with nitrogen, and normal pressure is heated to 800 ℃.In the time of 800 ℃, stop nitrogen and purge, the mixed vapour of methane (Matheson, 99.99% purity) and air (Matheson) feeds in the beds.The flow velocity that depends on these feed component, carbon/oxygen atom is than (being equivalent to 1/2 C/O 2Than) be 1.04-1.09, gas hourly space velocity (GHSV) is 17000-23000hr -1Each test all kept 48 hours under controlled condition.In this time, methane average conversion (except embodiment 15) is 86-89%, to partial oxidation products CO and H 2The mole selectivity greater than 97%.Among the embodiment 15, methane conversion is 75%, to CO and H 2The mole selectivity be respectively 87% and 93%.Use gas-chromatography that the gas-phase product of discharging reactor is carried out on-line analysis.Provided C/O in the table 11 than analyzing the carbon content that draws on the dead catalyst afterwards with each test.
Table 11
Embodiment Catalyst The C/O atomic ratio Dead catalyst coke formation rate weight %
11 Na-Ni-Sr-P-O (taking from embodiment 1) 1.09 1.1
12 Na-Ni-Ca-P-O (taking from embodiment 2) 1.09 0.4
13 Flooded the Na-Sr-P-O (taking from embodiment 4) of Ni 1.05 0.82
14 Na-Ni-La-Sr-P-O (taking from embodiment 6) 1.08 0.1
15 Na-Ni-Ca-Sr-P-O (taking from embodiment 8) 1.04 0.77
16 Commodity Ni/Al 2O 3 1.08 23.2
17 Commodity Ni/Al 2O 3-MgO helps catalysis 1.05 9.0
This studies show that the partial oxidation catalyst performance aspect conversion ratio and mole selectivity that falls into interior carbon monoxide-olefin polymeric (embodiment 11-15) of the scope of the invention and routine is suitable.Yet these catalyst can reduce coke surprisingly and form speed, also can clearly be seen that this point from accompanying drawing.The described outstanding characteristics of catalyst of the present invention allow it in industry continuity operation in service, and perhaps in (for example under higher C/O atomic ratio) operation under the more harsh condition, described more harsh condition can provide higher-quality synthesis gas product.

Claims (10)

1, carbon monoxide-olefin polymeric is used for preparing synthesis gas from light hydrocarbon, and this carbon monoxide-olefin polymeric comprises having chemical composition with based on anhydrous empirical formula:
A v(B t+) wNi xD(G u-) yO z
The crystal metal oxide component of expression, wherein A is selected from Li +, Na +, K +, Rb +, Cs +Alkali metal and composition thereof; " v " is the mol ratio of A to D, and size is 0-2; B is an alkalinous metal; " w " is the mol ratio of B to D, and size is 1-3; " t " is the weighted average chemical valence of B, and size is 2-3; " x " is the mol ratio of Ni to D, and size is 0-0.5; D is selected from P + 5, V + 5And composition thereof the skeleton component; G is selected from OH -, Cl -, F -, CO 3 2-And composition thereof anion; " u " is the average valence of G, and size is 1-2; " y " is the mol ratio of G to D, and size is 0-2; " z " is the mol ratio of O to D, and its numerical value is determined by following formula:
z＝(v+t·w+2·x+5-u·y)，
When B was Ca, " v " was not equal to 0, when " x " is 0, also comprised the nickel component that is dispersed on the crystal metal oxide component in the carbon monoxide-olefin polymeric.
2, the carbon monoxide-olefin polymeric of claim 1, wherein B is selected from Ca 2+, Sr 2+, Pb 2+, Cd 2+, Ba 2+, La 3+, Eu 3+, Gd 3+, Pr 3+, Nd 3+, Sm 3+, Y 3+, Yb 3+And composition thereof.
3, the carbon monoxide-olefin polymeric of claim 1, wherein the crystal metal oxide component has apatite or hydroxyapatite crystal structure.
4, the carbon monoxide-olefin polymeric of claim 1, when " x " greater than 0 the time, the nickel component is dispersed on the crystal metal oxide component.
5, the method for each carbon monoxide-olefin polymeric among the preparation claim 1-4 comprises:
A) make the mixture of the reactive sources material that contains B, nonessential Ni, D and nonessential A, be enough to form at pH value 8-14, temperature and time under the condition of crystal metal oxide component and react, the composition of mixture can be represented by following formula:
hA 2O:jBO t/2:kNiO:D 2O 5:1N:mH 2O
Wherein N is that a kind of mineralizer, " h " size are 40-500 for 0-1.0, " l " size for 0-20, " m " size for 0.10-6.0, " k " size for 0-10, " i " size;
B) when " k " is 0, the aqueous solution of crystal metal oxide component with nickel salt that is selected from nickel nitrate, nickel chloride, nickelous bromide, nickel acetate and composition thereof is contacted; With
C) with step (a) and crystal metal oxide component (b) 600 ℃-1000 ℃ temperature lower calcination 1-10 hour to make catalyst.
6, the method for claim 5, also comprise when " k " greater than 0 the time, steps performed (b).
7, the method for claim 5, wherein skeleton component D is a phosphorus, the reactive sources material is selected from phosphoric acid, pyrophosphoric acid, alkali metal phosphate, sodium metaphosphate and composition thereof.
8, a kind of method for preparing synthesis gas, the carbon monoxide-olefin polymeric that is included among the claim 1-4 each exists down, and light hydrocarbon and oxidant are reacted under reaction condition.
9, the method for claim 8, wherein said reaction is selected from partial oxidation, steam reformation, self-heating recapitalization and CO 2Reform.
10, the method for claim 10, wherein said oxidant comprise oxygen, air, enrichment air, steam, carbon dioxide and composition thereof; When oxidant comprises oxygen, air or enrichment air, reaction condition comprise carbon to the atomic ratio of oxygen be 0.5-2.0 and; When oxidant comprises steam, reaction condition comprise carbon to the mol ratio of steam less than 2.
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WO2014005347A1 (en) * 2012-07-05 2014-01-09 中国科学院大连化学物理研究所 Phosphide catalyst for synthesis gas conversion, preparation method and use thereof
CN106281464A (en) * 2016-08-29 2017-01-04 清华大学 A kind of method that methane and carbon dioxide catalytic reforming prepares synthesis gas
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CN113952970A (en) * 2021-11-10 2022-01-21 中国科学院山西煤炭化学研究所 Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof

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CN106281464B (en) * 2016-08-29 2020-04-10 清华大学 Method for preparing synthesis gas by catalytic reforming of methane and carbon dioxide
CN110860314A (en) * 2019-11-25 2020-03-06 湖南绿脉环保科技有限公司 Carbon catalytic oxidant and method for treating carbon-containing waste residue of electrolytic aluminum
CN110860314B (en) * 2019-11-25 2022-10-11 湖南绿脉环保科技股份有限公司 Carbon catalytic oxidant and method for treating carbon-containing waste residue of electrolytic aluminum
CN113952970A (en) * 2021-11-10 2022-01-21 中国科学院山西煤炭化学研究所 Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof

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