CN110064418A - A kind of oxidation state reforming catalyst and preparation method thereof - Google Patents
A kind of oxidation state reforming catalyst and preparation method thereof Download PDFInfo
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- CN110064418A CN110064418A CN201810063594.9A CN201810063594A CN110064418A CN 110064418 A CN110064418 A CN 110064418A CN 201810063594 A CN201810063594 A CN 201810063594A CN 110064418 A CN110064418 A CN 110064418A
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
- C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a kind of oxidation state reforming catalysts and preparation method thereof, which includes the following steps: step 1, prepare stanniferous alumina support；Step 2, the carrier of impregnation steps 1, dipping temperature are 10~50 DEG C, include compound containing platinum, rare earth compound, competitive adsorbate and nitrogenous compound in maceration extract；And the carrier drying after step 2 dipping, activation are obtained reforming catalyst by step 3；Wherein, on the basis of the gross mass of butt alumina support, reforming catalyst includes the platinum of 0.1~0.4 mass %, the tin of 0.1~0.6 mass %, the chlorine of the rare earth of 0.05~1 mass % and 0.3~3.0 mass %.Catalyst of the present invention is used for hydrocarbon catalytic reforming reaction, can reduce the generation of coke, improve the selectivity of aromatic hydrocarbon product.
Description
Technical field
The present invention is a kind of reforming catalyst and preparation method thereof, specifically, being a kind of oxidation state weight containing light rare earth
Whole catalyst and preparation method thereof.
Background technique
Catalytic reforming is one of important production technology of PETROLEUM PROCESSING, and main purpose is production high-knock rating gasoline, BTX
Aromatic hydrocarbons and cheap hydrogen.As the quality on gasoline and diesel upgrading and hydrogen addition technology are fast-developing, catalytic reforming is in oil-refining chemical row
Status in industry is more and more important.Currently, industrially commonly used reforming catalyst is the Pt- for semi regeneration reforming process
Re/A12O3Catalyst and Pt-Sn/A1 for cyclic regeneration reforming process2O3。
The index for usually measuring catalyst performance includes activity, selectivity and stability.It is living for reforming catalyst
Property under given raw material and reaction condition the size of products therefrom arene content or octane number, or give octane number under
The height of reaction temperature；Selectively refer under given activity level, the yield or C of aromatic hydrocarbons5 +The yield of gasoline products；Surely
The qualitative variation for referring to catalyst activity or selectivity under unit time or processed in units amount.High performance reforming catalyst should have
There are higher activity and selectivity and higher stability.
USP3915845 discloses a kind of more metal catalytic components of the hydrocarbon conversion, the Pt race including 0.01~2.0 weight %
Metal, the germanium of 0.01~5.0 weight %, 0.1~3.5 weight % halogen and lanthanide series compound.Lanthanide series is in catalyst
Lanthanum, cerium and neodymium.
USP4039477 discloses a kind of hydrotreating catalyst modified with lanthanide series metal and its application.The catalysis
Agent include a kind of refractory metal oxide, Pt race metal, Sn and it is at least one selected from Y, Th, U, Pr, Ce, La, Nd, Sm, Dy and
The metal of Gd.Lanthanide series metal is added in the patent in the catalyst, so that the activity stability of catalyst is improved, and tin is deposited
It is reduced in the lytic activity that can make the catalyst containing lanthanide series metal, is conducive to improve selectivity.
USP6059960 discloses a kind of Pt-Sn multimetal reforming catalyst containing rare earth, and the group of the lanthanides constituent element introduced is
The mixture of Eu, Yb, Sm or Eu and Yb, and 50% or more lanthanide series metal exists in the catalyst with EuO.When catalyst is equal
Pt-Sn-Eu group timesharing, only when Eu/Pt atomic ratio is 1.3~2.0, opposite activity and selectivity is preferable, and ratio is less than 1.3
When, the selectivity of catalyst reduces, and when ratio is greater than 2.0, catalytic activity is decreased obviously.
USP6007700 discloses a kind of reforming catalyst, the catalyst characteristics are as follows: carrier is by η-Al2O3With γ-Al2O3
Composition, at least one doping metals are selected from Ti, Zr, Hf, Co, Ni, Zn and lanthanide series metal, at least one halogens, at least one
Kind Pt race element and a kind of promoter metal are selected from Sn, Ge, In, Ga, Tl, Sb, Pb, Re, Mn, Cr, Mo and W.Due to the catalyst
Carrier be extrusion molding, catalyst is bar shaped.
CN 02809057 discloses platiniferous, the multimetal reforming catalyst of tin and its preparation and application, the group of the lanthanides introduced
Constituent element is Eu and Ce.The catalyst is used for the reforming reaction activity and selectivity with higher of naphtha, and coke deposit rate is low, the longevity
Life length.
CN 201310178694 discloses a kind of multimetal reforming catalyst, and catalyst 0.3 mass % containing Pt contains Sn
0.3 mass %, 0.1~0.5 mass % containing Y, 0.5~1.0 mass % containing Sm, 1.1~1.3 mass % containing chlorine.
CN 201410532295 discloses a kind of preparation method of multimetal reforming catalyst, including by uniform load platinum,
The catalyst pellet of tin and rare earth metal is contacted with the powder solid phase of rare earth metal salt, is then roasted in air or air contained water
It burns, rare earth metal average content of the obtained reforming catalyst in housing region is center region rare earth metal average content
2~5 times, the catalyst housing region refers to region of the catalyst pellet outer rim to center position with a thickness of 150um, catalyst
In the preferred europium of rare earth metal or samarium.
CN1715370A discloses a kind of preparation method of Pt-Sn- rare earth reforming catalyst, which adds in maceration extract
Enter suitable organic amine, to adjust the pH value of maceration extract, prevents rare earth metal to be lost in dipping process, while guaranteeing VIII group
Metal has enough load capacity in the carrier and is evenly distributed.
CN 201280029171 discloses a kind of catalyst of the catalytic reforming of naphtha.The catalyst can have
One of platinum, palladium, rhodium, ruthenium, hungry and iridium or a variety of noble metals include the one or more of periodic table atomic number 57-71
The lanthanide series metal and carrier of element.Lanthanide series metal: the atomic ratio of noble metal is less than 1.3:1.Lanthanide series metal can be with catalyst
Lanthanide series metal concentration in 100 μm of superficial layers is less than 2 times of distributions of the lanthanide series metal concentration at catalyst center core.
For the reforming catalyst haveing excellent performance, other than requiring Pt constituent element to be uniformly distributed on carrier, it is also necessary to Pt group
Member has compared with small particle, and hydrogenolysis and carbon deposit can be inhibited to react in this way.Analysis Pt particle size has chemisorption, Electronic Speculum, infrared etc.
Method.In addition, there are also a kind of fast and simple method H2- TPR method, although this method cannot obtain Pt particle size quantitative values,
Fixed TPR analysis condition, can qualitatively judge Pt particle size by reduction peak temperature, and higher reduction peak temperature correspondence is smaller
Pt partial size.
Existing reforming catalyst product has oxidation state, also there is reduction-state.For oxidized catalyst, catalyst manufacturer is not
Need to increase hydrogen reducing unit, catalyst is restored on refinery facilities.For reduction-state catalyst, catalyst is being produced
Factory is restored, and catalyst, which is packed into refinery facilities, directly to go into operation, but reduction-state catalyst storage process needs nitrogen protection,
Furthermore inevitably ingress of air needs to supplement reduction on device catalyst dress agent process if the catalyst storage time is long.
Summary of the invention
The main purpose of the present invention is to provide a kind of oxidation state reforming catalysts and preparation method thereof, to overcome existing skill
Catalyst platinum cluster partial size is larger in art, in catalytic reforming process caused by side reaction the problem of easy green coke carbon distribution.
In order to achieve the above object, the present invention provides a kind of preparation method of oxidation state reforming catalyst, the preparation sides
Method includes the following steps:
Step 1, stanniferous alumina support is prepared；
Step 2, the carrier of impregnation steps 1, dipping temperature are 10~50 DEG C, include compound containing platinum, rare earth in maceration extract
Compound, competitive adsorbate and nitrogenous compound；And
Step 3, by the carrier drying after step 2 dipping, activation, reforming catalyst is obtained；
Wherein, on the basis of the gross mass of butt alumina support, reforming catalyst includes the platinum of 0.1~0.4 mass %,
The tin of 0.1~0.6 mass %, the chlorine of the rare earth of 0.05~1.0 mass % and 0.3~3.0 mass %.
The preparation method of oxidation state reforming catalyst of the present invention, wherein the cl part in the reforming catalyst
Or all from competitive adsorbate, the competitive adsorbate preferably includes one of hydrochloric acid, dichloroacetic acid and trichloroacetic acid
Or it is several.
The preparation method of oxidation state reforming catalyst of the present invention, wherein the shape of the alumina support is preferred
For spherical shape.
The preparation method of oxidation state reforming catalyst of the present invention, wherein the compound containing platinum is preferably chlorine platinum
Acid, potassium chloroplatinate, ammonium chloroplatinate, platinum tetrachloride, in four the formed group of ammino platinum of platinum nitrate, four ammino platinum of chlorination and hydroxide
One or more.
The preparation method of oxidation state reforming catalyst of the present invention, wherein the rare earth compound is preferably lanthanum
Close one of object, cerium compound, praseodymium compound, neodymium compound, promethium compound, samarium compound and the formed group of europium compound
Or it is several.
The preparation method of oxidation state reforming catalyst of the present invention, wherein the rare earth compound is preferably nitric acid
In lanthanum, lanthanum chloride, cerous chlorate, cerous nitrate, cerous nitrate, praseodymium chloride, acetic acid neodymium, samarium trichloride and the formed group of europium nitrate
It is one or more of.
The preparation method of oxidation state reforming catalyst of the present invention, wherein the nitrogenous compound is preferably urea,
The amount of urea preferably accounts for 0.01~5.0 mass % of the gross mass of butt alumina support in the maceration extract.
The preparation method of oxidation state reforming catalyst of the present invention, wherein in the step 2, maceration extract and carrier
Liquid to consolidate volume ratio be preferably 0.5~3:1, dip time is preferably 0.1~4 hour.
The preparation method of oxidation state reforming catalyst of the present invention, wherein in the step 3, activation phenomenon is preferred
For air, activation temperature is preferably 200~650 DEG C, and activation time is preferably 0.5~10 hour.
In order to achieve the above object, the present invention also provides the preparations of the preparation method of above-mentioned oxidation state reforming catalyst
Catalyst.
Beneficial effects of the present invention:
The present invention joined nitrogenous compound, preferably urea in maceration extract, enhance the mutual of metal constituent element and carrier
Effect, metal constituent element is not easy to assemble, so that catalyst platinum cluster partial size is smaller；
Pt atom cluster partial size reduces, it is possible to reduce the generation of hydrogenolysis side reaction during reforming reaction reduces hydrogenolysis by-product
Object methane improves product arenes selectivity.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The present invention provides a kind of preparation method of oxidation state reforming catalyst, which includes the following steps:
Step 1, stanniferous alumina support is prepared；
Step 2, the carrier of impregnation steps 1, dipping temperature are 10~50 DEG C, include compound containing platinum, rare earth in maceration extract
Compound, competitive adsorbate and nitrogenous compound；And
Step 3, by the carrier drying after step 2 dipping, activation, reforming catalyst is obtained；
Wherein, on the basis of the gross mass of butt alumina support, reforming catalyst includes the platinum of 0.1~0.4 mass %,
The tin of 0.1~0.6 mass %, the chlorine of the rare earth of 0.05~1 mass % and 0.3~3.0 mass %.
The present invention is not particularly limited to the step of preparing stanniferous alumina support, as long as being able to satisfy demand of the invention
?.The shape of alumina support can be bar shaped, cloverleaf pattern or spherical shape, preferably spherical alumina support.Ball-aluminium oxide
Carrier can first can prepare spherical alumina support, then introduce Sn by dipping method by spin or drop ball preparation
Element, as introduced Sn element when spin or preparation drop spherocolloid, can also preferably exist in spherical alumina support preparation process
Sn element is introduced when dripping spherocolloid, on the basis of the gross mass of butt alumina support, the content of the Sn of addition is 0.1~0.6
Quality %.
Then, the stanniferous alumina support of preparation is impregnated into active component, dipping temperature is 10~50 DEG C.Maceration extract packet
Include compound containing platinum, rare earth compound, competitive adsorbate and nitrogenous compound.Compound containing platinum is chloroplatinic acid, potassium chloroplatinate, chlorine
One or more of platinic acid ammonium, platinum tetrachloride, four the formed group of ammino platinum of platinum nitrate, four ammino platinum of chlorination and hydroxide,
It is preferred that chloroplatinic acid.On the basis of the gross mass of butt alumina support, in maceration extract in compound containing platinum platinum content be 0.1~
0.4 mass %.Rare earth compound is preferably lanthanum compound, cerium compound, praseodymium compound, neodymium compound, promethium compound, samarium chemical combination
One or more of object and the formed group of europium compound；Further preferably lanthanum nitrate, lanthanum chloride, cerous chlorate, nitric acid
One or more of sub- cerium, cerous nitrate, praseodymium chloride, acetic acid neodymium, samarium trichloride and the formed group of europium nitrate.With butt aluminium oxide
On the basis of the gross mass of carrier, the content of rare earth is 0.05~1 mass % in maceration extract.Competitive adsorbate includes hydrochloric acid, dichloro
One or more of acetic acid and trichloroacetic acid preferably include the group of both trichloroacetic acid, hydrochloric acid or hydrochloric acid and trichloroacetic acid
It closes, on the basis of the gross mass of butt alumina support, the content of the chlorine in maceration extract in competitive adsorbate is 0.3~3.0 matter
Measure %.The nitrogenous compound is preferably urea, and the amount of urea preferably accounts for total matter of butt alumina support in the maceration extract
0.01~5.0 mass % of amount.
The interaction of metal constituent element and carrier can be enhanced in urea, so that metal constituent element is not easy to assemble, so that urging
Agent pt atom cluster partial size is smaller.If but dipping temperature is excessively high (for example dipping temperature is more than 75 DEG C), will lead in maceration extract
Hydrolysis of urea increases pH value, and Pt is caused to assemble, and Pt crystal grain is caused to become larger.
The present invention is not particularly limited impregnation method, if be able to satisfy the present invention claims active metal in carrying alumina
Load capacity on body.It can be also possible to supersaturated impregnation method for saturation impregnation method, the liquid of maceration extract and carrier is solid
Volume ratio is preferably 0.5~3:1.Dipping process can be static dipping, is also possible to dynamic and impregnates, and the dynamic dipping refers to
Rotating impregnation vessel in dipping process, preferably dynamic impregnate.Dipping temperature is 10~50 DEG C, and dip time is 0.1~4 hour.
The present invention, without filtering, is directly dried, activates, reduction treatment, being reformed to the mixture after dipping
Catalyst.Drying can be normal drying, is also possible to be dried in vacuo, preferably be dried in vacuo.Be dried in vacuo pressure be 0.001~
0.08MPa, vacuum drying temperature are 50~60 DEG C.Strict control vacuum drying temperature is needed, vacuum drying temperature is more than 75 DEG C,
It will lead to hydrolysis of urea in maceration extract, increase pH value, Pt is caused to assemble, Pt crystal grain is caused to become larger.
Activation of the present invention refers to roasts the catalyst after drying in activation phenomenon, and activation phenomenon is sky
Gas, activation temperature are 200~650 DEG C, and preferably 450~550 DEG C, activation time is 0.5~10 hour, preferably 1~4 hour.
The oxidation state reforming catalyst that the present invention obtains, on the basis of the gross mass of butt alumina support, Reforming catalyst
Agent includes the platinum of 0.1~0.4 mass %, the tin of 0.1~0.6 mass %, the rare earth and 0.3~3.0 matter of 0.05~1 mass %
Measure the chlorine of %.The catalyst is containing 5%H2Flowing Ar atmosphere in, carrying out TPR with 5 DEG C/min of heating rates, (temperature programming is also
It is former) test, the peak temperature of first reduction peak of Pt is greater than 260 DEG C.
Cl part in oxidation state reforming catalyst of the present invention or all from competitive adsorbate.
Catalyst of the present invention is suitable for naphtha reforming process, produces high-knock rating gasoline blend component or aromatic hydrocarbons.Stone brain
Oil is preferably rich in the oil product of cycloalkane and alkane, can be direct steaming gasoline, be hydrocracked heavy naphtha, thermal cracking or be catalyzed and split
The gasoline fraction and F- T synthesis gasoline of change.It is measured according to ASTMD-86 method, such as initial boiling point is 40~80 DEG C, the end point of distillation
For 160~220 DEG C of full boiling point gasoline, the scheelite brain that the light naphthar or boiling range that boiling range is 60~150 DEG C are 100~200 DEG C
Oil.
For catalyst of the present invention when being used for catalytic reforming reaction process, catalytic reforming reaction condition is for example are as follows: absolute pressure
For 100kPa~7MPa, preferably 0.35~2.5MPa；Reaction temperature is 315~600 DEG C, preferably 425~565 DEG C；Hydrogen/hydrocarbon rubs
You are than being 1~20, preferably 2~10；Liquid hourly space velocity (LHSV) (LHSV) is 0.1~10 hour-1, preferably 1~5 hour-1。
Catalytic reforming process carries out under conditions of substantially anhydrous.Feedstock oil water content when entering catalytic reforming zone of transformation
It should be less than 50ppm, more preferably less than 20ppm.Water in reforming raw oil can be by conventional adsorbent, as molecular sieve is done
It is dry, stripping operation appropriate can also be carried out by fractionating device to adjust, can also will be adsorbed by drying and strip certainly dry knot
It closes, to exclude the water in feedstock oil.
The content of Pt, Sn and rare earth X-ray fluorescence spectrometry, chlorinity determination of electrode in catalyst.
Technical solution of the present invention is further elaborated below by specific embodiment.
Embodiment 1
100 grams of boehmites (production of Sasol company) and appropriate amount of deionized water are taken, liquid/solid mass ratio is 2, and room temperature is stirred
Mix pulp 0.5 hour.Then the hydrochloric acid solution of the stannous chloride of 3 milliliters of nitric acid and predetermined amount is added, makes the amount containing Sn in solution
Opposite butt aluminium oxide is 0.30 mass %, is acidified 2 hours.Then ball forming is dripped in oil ammonia column, wet bulb solidifies 1 in ammonium hydroxide
Hour, then filter, be washed with deionized three times, 60 DEG C drying 6 hours, 120 DEG C drying 2 hours, in moving air atmosphere
In 650 DEG C roast 4 hours, obtain the alumina globule carrier containing Sn.
Predetermined amounts prepare containing chloroplatinic acid, cerous nitrate, hydrochloric acid, urea maceration extract, platinum content in maceration extract, cerium content,
HCl content and urea content are respectively 0.29%, 0.23%, 1.8% and 3.2% with respect to butt quality of alumina.Take the dipping
Walk the carrier of preparation on liquid dipping, the liquid/solid volume ratio of maceration extract and carrier is 1.8, and dipping temperature is 15 DEG C, dip time 1
Hour.Then, 2 hours dry at 120 DEG C after 60 DEG C are evaporated extra maceration extract under vacuum condition.Catalysis after drying
Agent precursor activates 4 hours in 500 DEG C of air, and catalyst A is made, and the composition of A is shown in Table 1.
Embodiment 2
Catalyst B is prepared as described in Example 1, the difference is that rare earth compound is europium nitrate in maceration extract, it is specific to walk
It is rapid as follows:
100 grams of boehmites (production of Sasol company) and appropriate amount of deionized water are taken, liquid/solid mass ratio is 2, and room temperature is stirred
Mix pulp 0.5 hour.Then the hydrochloric acid solution of the stannous chloride of 3 milliliters of nitric acid and predetermined amount is added, makes the amount containing Sn in solution
Opposite butt aluminium oxide is 0.30 mass %, is acidified 2 hours.Then ball forming is dripped in oil ammonia column, wet bulb solidifies 1 in ammonium hydroxide
Hour, then filter, be washed with deionized three times, 60 DEG C drying 6 hours, 120 DEG C drying 2 hours, in moving air atmosphere
In 650 DEG C roast 4 hours, obtain the alumina globule carrier containing Sn.
Predetermined amounts prepare containing chloroplatinic acid, europium nitrate, hydrochloric acid, urea maceration extract, platinum content in maceration extract, europium content,
HCl content and urea content are respectively 0.29%, 0.23%, 1.8% and 3.2% with respect to butt quality of alumina.Take the dipping
Walk the carrier of preparation on liquid dipping, the liquid/solid volume ratio of maceration extract and carrier is 1.8, and dipping temperature is 15 DEG C, dip time 1
Hour.Then, 2 hours dry at 120 DEG C after 60 DEG C are evaporated extra maceration extract under vacuum condition.Catalysis after drying
Agent precursor activates 4 hours in 500 DEG C of air, and catalyst B is made, and the composition of catalyst B is shown in Table 1.
Embodiment 3
Alumina globule carrier is prepared as described in Example 1, and Sn content is 0.40 matter with respect to butt aluminium oxide in carrier
Measure %.
Catalyst C is prepared as described in Example 1, the difference is that rare earth compound is cerous chlorate, dipping in maceration extract
In liquid platinum content, cerium content, HCl content and urea content with respect to butt quality of alumina be respectively 0.36%, 0.89%,
2.7% and 4.8%.It takes the maceration extract to impregnate and walks the carrier of preparation, the liquid/solid volume ratio of maceration extract and carrier is 1.3, dipping
Temperature is 30 DEG C, dip time 3 hours, the specific steps are as follows:
100 grams of boehmites (production of Sasol company) and appropriate amount of deionized water are taken, liquid/solid mass ratio is 2, and room temperature is stirred
Mix pulp 0.5 hour.Then the hydrochloric acid solution of the stannous chloride of 3 milliliters of nitric acid and predetermined amount is added, makes the amount containing Sn in solution
Opposite butt aluminium oxide is 0.40 mass %, is acidified 2 hours.Then ball forming is dripped in oil ammonia column, wet bulb solidifies 1 in ammonium hydroxide
Hour, then filter, be washed with deionized three times, 60 DEG C drying 6 hours, 120 DEG C drying 2 hours, in moving air atmosphere
In 650 DEG C roast 4 hours, obtain the alumina globule carrier containing Sn.
Predetermined amounts prepare containing chloroplatinic acid, cerous chlorate, hydrochloric acid, urea maceration extract, platinum content, cerium contain in maceration extract
Amount, HCl content and urea content are respectively 0.36%, 0.89%, 2.7% and 4.8% with respect to butt quality of alumina.Take the leaching
Walk the carrier of preparation on stain liquid dipping, the liquid/solid volume ratio of maceration extract and carrier is 1.3, and dipping temperature is 30 DEG C, dip time
3 hours.Then, 2 hours dry at 120 DEG C after 60 DEG C are evaporated extra maceration extract under vacuum condition.Urging after drying
Agent precursor activates 4 hours in 500 DEG C of air, and catalyst C is made, and the composition of catalyst C is shown in Table 1.
Embodiment 4
Alumina globule carrier is prepared as described in Example 1, and Sn content is 0.24 matter with respect to butt aluminium oxide in carrier
Measure %.
Catalyst D is prepared as described in Example 1, the difference is that rare earth compound is lanthanum nitrate, maceration extract in maceration extract
Middle platinum content, lanthanum content, HCl content and urea content with respect to butt quality of alumina be 0.23%, 0.31%,
3.0% and 0.01%.The liquid/solid volume ratio of maceration extract and carrier is 1.8, and dipping temperature is 40 DEG C, dip time 0.1 hour.
Under vacuum condition, 50 DEG C are evaporated extra maceration extract.Specific step is as follows:
100 grams of boehmites (production of Sasol company) and appropriate amount of deionized water are taken, liquid/solid mass ratio is 2, and room temperature is stirred
Mix pulp 0.5 hour.Then the hydrochloric acid solution of the stannous chloride of 3 milliliters of nitric acid and predetermined amount is added, makes the amount containing Sn in solution
Opposite butt aluminium oxide is 0.24 mass %, is acidified 2 hours.Then ball forming is dripped in oil ammonia column, wet bulb solidifies 1 in ammonium hydroxide
Hour, then filter, be washed with deionized three times, 60 DEG C drying 6 hours, 120 DEG C drying 2 hours, in moving air atmosphere
In 650 DEG C roast 4 hours, obtain the alumina globule carrier containing Sn.
Predetermined amounts prepare containing chloroplatinic acid, lanthanum nitrate, hydrochloric acid, urea maceration extract, platinum content in maceration extract, lanthanum content,
HCl content and urea content are respectively 0.23%, 0.31%, 3.0% and 0.01% with respect to butt quality of alumina.Take the dipping
Walk the carrier of preparation on liquid dipping, the liquid/solid volume ratio of maceration extract and carrier is 1.8, and dipping temperature is 40 DEG C, dip time
0.1 hour.Then, 2 hours dry at 120 DEG C after 50 DEG C are evaporated extra maceration extract under vacuum condition.After drying
Catalyst precarsor activates 4 hours in 500 DEG C of air, and catalyst D is made, and the composition of catalyst D is shown in Table 1.
Embodiment 5
Catalyst E is prepared as described in Example 4, the difference is that rare earth compound is praseodymium chloride, maceration extract in maceration extract
Middle praseodymium content and urea content are respectively 0.46% and 2.6% with respect to butt quality of alumina.The liquid/solid body of maceration extract and carrier
Product is than being 1.4.Specific step is as follows:
100 grams of boehmites (production of Sasol company) and appropriate amount of deionized water are taken, liquid/solid mass ratio is 2, and room temperature is stirred
Mix pulp 0.5 hour.Then the hydrochloric acid solution of the stannous chloride of 3 milliliters of nitric acid and predetermined amount is added, makes the amount containing Sn in solution
Opposite butt aluminium oxide is 0.24 mass %, is acidified 2 hours.Then ball forming is dripped in oil ammonia column, wet bulb solidifies 1 in ammonium hydroxide
Hour, then filter, be washed with deionized three times, 60 DEG C drying 6 hours, 120 DEG C drying 2 hours, in moving air atmosphere
In 650 DEG C roast 4 hours, obtain the alumina globule carrier containing Sn.
Predetermined amounts prepare containing chloroplatinic acid, praseodymium chloride, hydrochloric acid, urea maceration extract, platinum content in maceration extract, praseodymium content,
HCl content and urea content are respectively 0.23%, 0.46%, 3.0% and 2.6% with respect to butt quality of alumina.Take the dipping
Walk the carrier of preparation on liquid dipping, the liquid/solid volume ratio of maceration extract and carrier is 1.4, and dipping temperature is 40 DEG C, dip time
0.1 hour.Then, 2 hours dry at 120 DEG C after 50 DEG C are evaporated extra maceration extract under vacuum condition.After drying
Catalyst precarsor activates 4 hours in 500 DEG C of air, and catalyst E is made, and the composition of catalyst E is shown in Table 1.
Embodiment 6
Catalyst F is prepared as described in Example 5, the difference is that rare earth compound is samarium trichloride, maceration extract in maceration extract
Middle samarium content and urea content are 0.12% and 1.5% with respect to butt quality of alumina.Specific step is as follows:
100 grams of boehmites (production of Sasol company) and appropriate amount of deionized water are taken, liquid/solid mass ratio is 2, and room temperature is stirred
Mix pulp 0.5 hour.Then the hydrochloric acid solution of the stannous chloride of 3 milliliters of nitric acid and predetermined amount is added, makes the amount containing Sn in solution
Opposite butt aluminium oxide is 0.24 mass %, is acidified 2 hours.Then ball forming is dripped in oil ammonia column, wet bulb solidifies 1 in ammonium hydroxide
Hour, then filter, be washed with deionized three times, 60 DEG C drying 6 hours, 120 DEG C drying 2 hours, in moving air atmosphere
In 650 DEG C roast 4 hours, obtain the alumina globule carrier containing Sn.
Predetermined amounts prepare containing chloroplatinic acid, samarium trichloride, hydrochloric acid, urea maceration extract, platinum content in maceration extract, samarium content,
HCl content and urea content are respectively 0.23%, 0.12%, 3.0% and 1.5% with respect to butt quality of alumina.Take the dipping
Walk the carrier of preparation on liquid dipping, the liquid/solid volume ratio of maceration extract and carrier is 1.4, and dipping temperature is 40 DEG C, dip time
0.1 hour.Then, 2 hours dry at 120 DEG C after 50 DEG C are evaporated extra maceration extract under vacuum condition.After drying
Catalyst precarsor activates 4 hours in 500 DEG C of air, and catalyst F is made, and the composition of catalyst F is shown in Table 1.
Embodiment 7
Catalyst G is prepared as described in Example 5, the difference is that rare earth compound is acetic acid neodymium, maceration extract in maceration extract
Middle neodymium content and urea content are 0.18% and 1.9% with respect to butt quality of alumina.Specific step is as follows:
100 grams of boehmites (production of Sasol company) and appropriate amount of deionized water are taken, liquid/solid mass ratio is 2, and room temperature is stirred
Mix pulp 0.5 hour.Then the hydrochloric acid solution of the stannous chloride of 3 milliliters of nitric acid and predetermined amount is added, makes the amount containing Sn in solution
Opposite butt aluminium oxide is 0.24 mass %, is acidified 2 hours.Then ball forming is dripped in oil ammonia column, wet bulb solidifies 1 in ammonium hydroxide
Hour, then filter, be washed with deionized three times, 60 DEG C drying 6 hours, 120 DEG C drying 2 hours, in moving air atmosphere
In 650 DEG C roast 4 hours, obtain the alumina globule carrier containing Sn.
Predetermined amounts prepare containing chloroplatinic acid, acetic acid neodymium, hydrochloric acid, urea maceration extract, platinum content in maceration extract, neodymium content,
HCl content and urea content are respectively 0.23%, 0.18%, 3.0% and 1.9% with respect to butt quality of alumina.Take the dipping
Walk the carrier of preparation on liquid dipping, the liquid/solid volume ratio of maceration extract and carrier is 1.4, and dipping temperature is 40 DEG C, dip time
0.1 hour.Then, 2 hours dry at 120 DEG C after 50 DEG C are evaporated extra maceration extract under vacuum condition.After drying
Catalyst precarsor activates 4 hours in 500 DEG C of air, and catalyst G is made, and the composition of catalyst G is shown in Table 1.
Embodiment 8
Alumina globule carrier is prepared as described in Example 1, and Sn content is 0.12 matter with respect to butt aluminium oxide in carrier
Measure %.
Catalyst H is prepared as described in Example 1, the difference is that rare earth compound is lanthanum chloride and protochloride in maceration extract
Cerium, lanthanum content, cerium content and urea content are respectively 0.07%, 0.07% and with respect to butt quality of alumina in maceration extract
0.8%.Specific step is as follows:
100 grams of boehmites (production of Sasol company) and appropriate amount of deionized water are taken, liquid/solid mass ratio is 2, and room temperature is stirred
Mix pulp 0.5 hour.Then the hydrochloric acid solution of the stannous chloride of 3 milliliters of nitric acid and predetermined amount is added, makes the amount containing Sn in solution
Opposite butt aluminium oxide is 0.12 mass %, is acidified 2 hours.Then ball forming is dripped in oil ammonia column, wet bulb solidifies 1 in ammonium hydroxide
Hour, then filter, be washed with deionized three times, 60 DEG C drying 6 hours, 120 DEG C drying 2 hours, in moving air atmosphere
In 650 DEG C roast 4 hours, obtain the alumina globule carrier containing Sn.
Predetermined amounts prepare containing chloroplatinic acid, lanthanum chloride, cerous chlorate, hydrochloric acid, urea maceration extract, platinum contains in maceration extract
Amount, lanthanum content, cerium content, HCl content and urea content with respect to butt quality of alumina be respectively 0.17%, 0.07%,
0.07%, 1.6% and 0.8%.It takes the maceration extract to impregnate and walks the carrier of preparation, the liquid/solid volume ratio of maceration extract and carrier is
1.8, dipping temperature is 15 DEG C, dip time 1 hour.Then, under vacuum condition, after 60 DEG C are evaporated extra maceration extract,
It is 2 hours dry at 120 DEG C.Catalyst precarsor after drying activates 4 hours in 500 DEG C of air, and catalyst H, catalyst H is made
Composition table 1.
Comparative example 1~3
Catalyst is prepared by embodiment 1,3,6, the difference is that being free of urea in maceration extract.Catalyst P, Q, R composition is made
It is shown in Table 1.
Comparative example 4
Catalyst is prepared by embodiment 2, the difference is that 85 DEG C are evaporated extra maceration extract under vacuum condition.It is made
Catalyst S composition is shown in Table 1.
Comparative example 5
Catalyst S is prepared by 5 method of embodiment in patent CN 02809057, takes carrier containing Sn made from above-described embodiment 1
It 100 grams, is prepared with 180 milliliters of predetermined amounts and is impregnated containing the maceration extract of cerous nitrate and europium nitrate, cerium content, europium content in maceration extract
Opposite butt quality of alumina is respectively 0.49% and 0.16%.After dipping temperature is 25 DEG C, dip time 24 hours, institute is filtered
Solid is 6 hours dry in 60 DEG C, 120 DEG C after drying 10 hours, then in the air containing 2~3% vapor 600 DEG C roast
4 hours.
The mixed liquor of chloroplatinic acid, hydrochloric acid and trichloroacetic acid that carrier made from upper step is prepared with predetermined amounts impregnates, and mixes
Platinum content, HCl content and the trichloroacetic acid content closed in liquid are divided into 0.31%, 1.2% and with respect to butt quality of alumina
5.0%, the liquid/solid volume ratio for impregnating mixed liquor and carrier is 1.8, dip time 24 hours.Solid is at 510 DEG C after immersion filtration
Water/HC1 molar ratio is activated 6 hours obtained catalyst T under conditions of being 60:1 in air, and the composition of T is shown in Table 1.
Comparative example 6
Salic carrier is prepared according to the method for embodiment 1, the difference is that stannic chloride is replaced with stannic chloride and Europium chloride,
On the basis of the gross mass of butt alumina support, the content of tin is 0.30 mass % in carrier, the content of europium is 0.20 matter
Measure %.
Catalyst U is prepared by patent CN1715370A method, takes 100 grams of above-mentioned carrier, contains ethanol amine, salt with 180 milliliters
The solution of acid and chloroplatinic acid impregnates, in maceration extract platinum content and HCl content with respect to butt quality of alumina be respectively 0.29%,
2.5%, the ratio of the amount of the substance of ethanol amine and HCl is 0.39.Dip time be 24 hours, with acidproof filter tunnel by mother liquor with
Solid separation, solid is 5 hours dry at 120 DEG C, and 510 DEG C in H2O/HCl molecular proportion is water chlorine activation processing 3 in the air of 40:1
Hour, catalyst U obtained, the composition of U is shown in Table 1.
Wherein, urea content refers to the amount Zhan Gan of urea in maceration extract in the maceration extract mentioned in each embodiment and comparative example
The percentage of base alumina support gross mass.
The composition of 1 catalyst of table
Embodiment 9
The present embodiment carries out the TPR analysis of catalyst.
It is Micromeritics AutoChem 2920 that catalyst TPR, which analyzes instrument,.The pretreatment condition of sample:
It takes 0.5 gram of catalyst to be packed into U-shaped quartz ampoule and is warming up to 400 DEG C in the He air-flow of flow velocity 50mL/min with 10 DEG C/min, in advance
Handle 2h.It is cooled to room temperature, then in the 5%H of flow velocity 30mL/min2650 DEG C are warming up in-Ar air-flow, heating rate 5
℃/min.The peak temperature for recording first reduction peak of catalyst Pt, the results are shown in Table 2.
The peak temperature of first reduction peak of 2 catalyst Pt of table
Table 2 is the result shows that catalyst prepared by the present invention, since metal constituent element partial size is smaller, the phase of metal constituent element and carrier
Interaction is stronger, and the initial reduction temperature of respective metal constituent element is higher.
Embodiment 10
The present embodiment evaluates the performance of the embodiment of the present invention and comparative example catalyst.
In micro-reactor, it is packed into 2 grams of catalyst, catalyst pretreatment condition are as follows: be passed through dry air, volume space velocity
700h-1, in 250 DEG C, 480 DEG C of each constant temperature 1h, nitrogen displacement is qualified, leads to 480 DEG C of reductase 12 h of hydrogen, volume space velocity 500h-1.It urges
Agent evaluation condition are as follows: using normal heptane as raw material, reaction temperature is 470 DEG C, reaction pressure 0.80MPa, mass space velocity 2h-1, hydrogen/hydrocarbon molar ratio is 3, and the reaction time is 22 hours, and reaction product on-line chromatograph analysis, chromatography is 6890 gas phase color of Agilent
Spectrum, is furnished with fid detector and capillary chromatograph, and evaluation result is shown in Table 3.
Conversion ratio X=(C7 I-C7 o)/C7 I,
C7 IFor reactor inlet normal heptane concentration,
C7 oFor reactor outlet normal heptane concentration.
Selectivity
YiFor i component yield,
X is normal heptane conversion ratio.
3 evaluating catalyst result of table
As can be seen from Table 3, compared with the catalyst of comparative example preparation, the catalyst activity of preparation of the embodiment of the present invention
Height, the arenes selectivity for being catalyzed products obtained therefrom is high, and isomerization product selectivity is high；Compared with the catalyst of comparative example preparation, this
The catalyst of invention preparation reduces the generation of hydrogenolysis side reaction, and hydrogenolysis product methane is reduced；With urging for comparative example preparation
Agent is compared, and catalyst prepared by the present invention reduces cracking reaction, and crackate C3~C4 is reduced.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (10)
1. a kind of preparation method of oxidation state reforming catalyst, which is characterized in that the preparation method includes the following steps:
Step 1, stanniferous alumina support is prepared；
Step 2, the carrier of impregnation steps 1, dipping temperature are 10~50 DEG C, include compound containing platinum, rare earth chemical combination in maceration extract
Object, competitive adsorbate and nitrogenous compound；And
Step 3, by the carrier drying after step 2 dipping, activation, reforming catalyst is obtained；
Wherein, on the basis of the gross mass of butt alumina support, reforming catalyst includes the platinum of 0.1~0.4 mass %, and 0.1
The tin of~0.6 mass %, the chlorine of the rare earth of 0.05~1.0 mass % and 0.3~3.0 mass %.
2. the preparation method of oxidation state reforming catalyst according to claim 1, which is characterized in that the reforming catalyst
In cl part or all from competitive adsorbate, the competitive adsorbate includes in hydrochloric acid, dichloroacetic acid and trichloroacetic acid
One or more.
3. the preparation method of oxidation state reforming catalyst according to claim 1, which is characterized in that the alumina support
Shape be spherical shape.
4. the preparation method of oxidation state reforming catalyst according to claim 1, which is characterized in that the compound containing platinum
It is made of chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate, platinum tetrachloride, platinum nitrate, four ammino platinum of chlorination and four ammino platinum of hydroxide
One or more of group.
5. the preparation method of oxidation state reforming catalyst according to claim 1, which is characterized in that the rare earth compound
It is made of in group lanthanum compound, cerium compound, praseodymium compound, neodymium compound, promethium compound, samarium compound and europium compound
One or more.
6. the preparation method of oxidation state reforming catalyst according to claim 5, which is characterized in that the rare earth compound
In groups by lanthanum nitrate, lanthanum chloride, cerous chlorate, cerous nitrate, cerous nitrate, praseodymium chloride, acetic acid neodymium, samarium trichloride and europium nitrate group
One or more of group.
7. the preparation method of oxidation state reforming catalyst according to claim 1, which is characterized in that the nitrogenous compound
For urea, the amount of urea accounts for 0.01~5.0 mass % of the gross mass of butt alumina support in the maceration extract.
8. the preparation method of oxidation state reforming catalyst according to claim 1, which is characterized in that in the step 2, leaching
It is 0.5~3:1 that the liquid of stain liquid and carrier, which consolidates volume ratio, and dip time is 0.1~4 hour.
9. the preparation method of oxidation state reforming catalyst according to claim 1, which is characterized in that living in the step 3
Change atmosphere is air, and activation temperature is 200~650 DEG C, and activation time is 0.5~10 hour.
10. catalyst prepared by the preparation method of oxidation state reforming catalyst described in claim 1 to 9 any one.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111003895A (en) * | 2019-12-27 | 2020-04-14 | 南京工业大学 | MTO chemical wastewater membrane method zero-discharge treatment process and waste salt resource utilization technology |
| CN111659428A (en) * | 2020-06-16 | 2020-09-15 | 四川润和催化新材料股份有限公司 | Continuous reforming catalyst and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535176A (en) * | 2001-04-28 | 2004-10-06 | �й�ʯ�ͻ����ɷ�����˾ | Multi metal reforming catalyst containing platinum, tin and its preparation and application |
| CN1935368A (en) * | 2006-09-06 | 2007-03-28 | 天津化工研究设计院 | Method for preparing purifying catalyst for reducing cold-start exhaust emission |
| CN101468313A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for preparing reforming catalyst |
| CN101623634A (en) * | 2009-08-04 | 2010-01-13 | 厦门大学 | Nuclear shell nanometer catalyst packaged with noble metal nanometer grains and method thereof |
| US20110065025A1 (en) * | 2009-08-10 | 2011-03-17 | Korea University Research And Business Foundation | Process of preparing pt/support or pt alloy/support catalyst, thus-prepared catalyst and fuel cell comprising the same |
| CN102332588A (en) * | 2011-10-17 | 2012-01-25 | 哈尔滨工业大学 | Method for preparing anode of solid oxide fuel cell by using immersion method |
| US20140045953A1 (en) * | 2012-08-07 | 2014-02-13 | Oxford Catalysts Limited | Treating of catalyst support |
| CN103816894A (en) * | 2014-02-17 | 2014-05-28 | 武汉科技大学 | Pt-Ru alloy nano electro-catalyst having doped graphene carrier and preparation method thereof |
| CN104148120A (en) * | 2014-06-19 | 2014-11-19 | 北京化工大学 | Method for controlling high dispersion of metal centers for catalysts by using auxiliaries |
| CN106391107A (en) * | 2015-08-03 | 2017-02-15 | 南开大学 | Hydroisomerization and cracking catalyst for preparation of biological aviation kerosene from castor oil |
| CN106669735A (en) * | 2016-12-27 | 2017-05-17 | 常州大学 | Catalyst for enhancing ammonia conversion in domestic wastewater, and application method thereof |
| CN107108206A (en) * | 2014-12-01 | 2017-08-29 | 沙特基础工业全球技术公司 | It is used for the application of the CO 2 reformation of methane by homogeneous deposition precipitation synthesis trimetal nanoparticles, and loaded catalyst |
| CN107537571A (en) * | 2017-10-23 | 2018-01-05 | 南京工程学院 | A kind of multi-walled carbon nanotube noble metal catalyst and preparation method thereof |
-
2018
- 2018-01-23 CN CN201810063594.9A patent/CN110064418B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535176A (en) * | 2001-04-28 | 2004-10-06 | �й�ʯ�ͻ����ɷ�����˾ | Multi metal reforming catalyst containing platinum, tin and its preparation and application |
| CN1935368A (en) * | 2006-09-06 | 2007-03-28 | 天津化工研究设计院 | Method for preparing purifying catalyst for reducing cold-start exhaust emission |
| CN101468313A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Method for preparing reforming catalyst |
| CN101623634A (en) * | 2009-08-04 | 2010-01-13 | 厦门大学 | Nuclear shell nanometer catalyst packaged with noble metal nanometer grains and method thereof |
| US20110065025A1 (en) * | 2009-08-10 | 2011-03-17 | Korea University Research And Business Foundation | Process of preparing pt/support or pt alloy/support catalyst, thus-prepared catalyst and fuel cell comprising the same |
| CN102332588A (en) * | 2011-10-17 | 2012-01-25 | 哈尔滨工业大学 | Method for preparing anode of solid oxide fuel cell by using immersion method |
| US20140045953A1 (en) * | 2012-08-07 | 2014-02-13 | Oxford Catalysts Limited | Treating of catalyst support |
| CN103816894A (en) * | 2014-02-17 | 2014-05-28 | 武汉科技大学 | Pt-Ru alloy nano electro-catalyst having doped graphene carrier and preparation method thereof |
| CN104148120A (en) * | 2014-06-19 | 2014-11-19 | 北京化工大学 | Method for controlling high dispersion of metal centers for catalysts by using auxiliaries |
| CN107108206A (en) * | 2014-12-01 | 2017-08-29 | 沙特基础工业全球技术公司 | It is used for the application of the CO 2 reformation of methane by homogeneous deposition precipitation synthesis trimetal nanoparticles, and loaded catalyst |
| CN106391107A (en) * | 2015-08-03 | 2017-02-15 | 南开大学 | Hydroisomerization and cracking catalyst for preparation of biological aviation kerosene from castor oil |
| CN106669735A (en) * | 2016-12-27 | 2017-05-17 | 常州大学 | Catalyst for enhancing ammonia conversion in domestic wastewater, and application method thereof |
| CN107537571A (en) * | 2017-10-23 | 2018-01-05 | 南京工程学院 | A kind of multi-walled carbon nanotube noble metal catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FENG JUN-TING ET AL.: "Enhancement of Metal Dispersion and Selective Acetylene Hydrogenation Catalytic Properties of a Supported Pd Catalyst", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 》 * |
| 段媛媛等: "分等级结构对锡氧化物负载Pt室温催化甲醛氧化性能的影响（英文）", 《催化学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111003895A (en) * | 2019-12-27 | 2020-04-14 | 南京工业大学 | MTO chemical wastewater membrane method zero-discharge treatment process and waste salt resource utilization technology |
| CN111659428A (en) * | 2020-06-16 | 2020-09-15 | 四川润和催化新材料股份有限公司 | Continuous reforming catalyst and preparation method and application thereof |
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