CN104667912A - Catalyst for CO dehydrogenation fluidized bed reaction and preparation method and application thereof - Google Patents
Catalyst for CO dehydrogenation fluidized bed reaction and preparation method and application thereof Download PDFInfo
- Publication number
- CN104667912A CN104667912A CN201410327115.1A CN201410327115A CN104667912A CN 104667912 A CN104667912 A CN 104667912A CN 201410327115 A CN201410327115 A CN 201410327115A CN 104667912 A CN104667912 A CN 104667912A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- dehydrogenation
- palladium
- fluidized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a catalyst for CO dehydrogenation fluidized bed reaction and a preparation method thereof as well as an application technology of the catalyst in a fluidized bed. The chemical formula of the catalyst provided by the invention is PdO/Al2O3, wherein PdO is an active component, and the mass of Pd accounts for 0.05-3.0 percent of that of the catalyst; Al2O3 serves as a carrier and is spherical particles with the diameter of 0.5-2.5mm; the specific surface area is 200-400m<2>/g, the bulk density is 0.5-0.9g/ml, the tensile strength is greater than or equal to 50N/particle, and the mass abrasion is less than or equal to 0.4 percent. The catalyst is used in a CO dehydrogenation fluidized bed reaction process and can remove a small amount of H2 in CO feed gas to be below 50ppm; compared with the prior art, the reaction technology disclosed by the invention is high in heat removing speed and stable in reaction temperature; flying temperature is avoided, the service life of the catalyst is prolonged, and the reaction airspeed can be increased; the catalyst is convenient to fill, and the problem of amplification of a CO feed gas dehydrogenation reaction single reactor in a technology for preparing ethylene glycol from coal can be effectively solved.
Description
Technical field
The present invention relates to a kind of catalyst preparation technology, be specifically related to CO dehydrogenation fluidized-bed reaction Catalysts and its preparation method and the technique for applying in fluid bed thereof, this catalyst has the feature of high intensity wear-resistant.
Background technology
To be separated through pressure-variable adsorption by the industrial tail gas such as coke oven factory, calcium carbide factory, steel mill or water-gas or cryogenics is separated the feed gas containing carbon monoxide body that obtains unavoidably with a certain amount of H
2remaining (content about 0.1 – 5.0%), this part a small amount of H
2follow-up oxonation can be affected, for ensureing that the efficient stable of oxonation runs, must first H a small amount of in feed gas containing carbon monoxide body
2remove.
At present, the method for dehydrogenating that domestic and international each research unit uses is the O by adding metering
2, under the effect of noble metal catalyst, a small amount of H under certain reaction temperature in selective oxidation removing CO
2.The reaction of feed gas containing carbon monoxide oxidative dehydrogenation is divided into main reaction and side reaction, main reaction: 2H
2+ O
2=2H
2o, side reaction: 2CO+O
2=2CO
2.
In world head cover 200,000 tons/year of coal-ethylene glycol industrial demonstration unit, feed gas containing carbon monoxide De-hydrogen Technology adopts Pd catalyst, carrier is aluminium oxide, adopt reactor be calandria type fixed bed reactor (coal-ethylene glycol technical progress [P]. chemical industry be in progress, 2010,29,2003-2009).
The reactor adopted in patent CN200910061853 is calandria type fixed bed reactor, its catalyst is a class Pt and/or Pd catalyst, carrier is aluminium oxide, and auxiliary agent for select 2-4 kind from sodium, potassium, magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten or cerium.
Patent CN201010147051 reports a kind of compound fixed bed reactors, adopt catalyst I and the catalyst I I of two kinds of different palladium load capacity, the weight percentage of the active component of catalyst I is 0.01 – 0.1%, the weight percentage of the active component of catalyst I I is 0.1 – 1.5%, and carrier is at least one in silica, aluminium oxide or molecular sieve.
But above-mentioned reactor is all calandria type fixed bed reactor, due to CO, H
2and O
2catalyst combustion reaction be strong exothermal reaction, need in time reaction heat is removed, and fixed bed reactors to move thermal effect general, easy temperature runaway in large commercial plant, makes the air speed of oxidative dehydrogenation be restricted, and air speed generally all controls at 5000h
-1below.The volume that strong exothermal reaction also limit single reactor amplifies, and in current industrialized coal-ethylene glycol technology, dehydrogenation reactor adopts the connection in series-parallel of many cover reactors to control reaction heat.
Fluidized-bed reactor has the following advantages: 1) motion of catalyst granules makes bed have good mass-and heat-transfer performance, and bed internal pressure drops is little, homogeneous temperature, and is easy to control, and is specially adapted to strong exothermal reaction; 2) be convenient to decaying catalyst discharge in time and regenerate, reaction can be carried out continuously, avoid existing fixed bed reactors more catalyst changeout time parking problem.But due to the hard hit of solid catalyst in flow process and friction, make catalyst accelerate efflorescence, therefore, have higher requirement to the compression strength of catalyst and wear extent.
Therefore, develop and be a kind ofly applicable to carry out in fluidized-bed reactor the high strength of oxidative dehydrogenation and the catalyst of low wear extent, effectively can improve the service life of Oxydehydrogenation catalyst, solve a difficult problem for the fixed bed reactors volume amplification adopted at present, Development of Coal preparing ethylene glycol technology is significant.
Summary of the invention
The object of this invention is to provide a kind of CO dehydrogenation fluidized-bed reaction Catalysts and its preparation method and the technique for applying of this catalyst in fluid bed.
Catalyst provided by the invention, its chemical formula is PdO/Al
2o
3, wherein PdO is active component, and the mass percentage that Pd accounts for catalyst is 0.05 – 3.0%, and preferably content is 0.2 – 0.5%; Al
2o
3for carrier, be the spheric granules of diameter 0.5 – 2.5mm, preferably diameter is 0.8 – 1.0mm, and its specific area is 200 – 400m
2/ g, preferably specific area is 250 – 300m
2/ g, bulk density is 0.5 – 0.9g/ml, and preferably bulk density is 0.7 – 0.8g/ml, compression strength>=50N/, and preferably compression strength is 80 – 120N/, Mass Loss≤0.4%, and preferably Mass Loss is 0.05 – 0.1%.Mass Loss is at room temperature, allows carrier in fluid bed according to the powder wear extent detected after simulated experiment condition flowing 24h.
The preparation method of catalyst provided by the invention, concrete steps are:
Soluble palladium salt is dissolved in diluted acid, then with Al
2o
3incipient impregnation, wherein the consumption of palladium salt is that 0.05 – 3.0% determines by carrying Pd mass percentage in palladium rear catalyst, and preferably content is 0.2 – 0.5%, by carrier A l
2o
3being immersed in dipping solution makes palladium salt fully be impregnated on carrier, leaches, and in 100 –, 200 DEG C of dryings, preferably baking temperature is 130 – 160 DEG C; After drying in Muffle furnace in air atmosphere in 350 –, 600 DEG C of roasting 8 – 24h, preferably sintering temperature is 450 – 500 DEG C, obtains PdO/Al
2o
3catalyst.Described soluble palladium salt is the one in palladium nitrate, palladium, palladium acetylacetonate, palladium bromide, palladium bichloride; One in the hydrochloric acid of described diluted acid to be concentration be 0.05 – 0.1M, nitric acid, sulfuric acid, acetic acid, hydrobromic acid.
Catalyst of the present invention carries out CO oxidative dehydrogenation in fluidized bed plant, by the O of feed gas containing carbon monoxide and metering
2enter gas distributor fully mix laggard enter fluidized-bed reactor, agitate PdO/Al
2o
3catalyst carries out oxidative dehydrogenation to riser, and reacted material enters cyclone separator and is separated, and gas-phase product goes out reaction tube from gas vent, dust and a small amount of PdO/Al
2o
3catalyst enters down-comer, can a small amount of H in feed gas containing carbon monoxide after reaction
2be removed to below 50ppm; Catalyst after inactivation is discharged from exit, down-comer lower end, and fresh catalyst and regenerated catalyst supplement from down-comer lower inlet.Through long-play examination, this PdO/Al
2o
3the life-span of catalyst is greater than 3000h.
In described feed gas containing carbon monoxide, CO volumn concentration is 50 – 99.5%, and preferably content is 96 – 99.5%, H
2volumn concentration is 0.1 – 10%, and preferably content is 0.5 – 4%.The amount of oxygen wherein added is V according to the volume ratio of hydrogen and oxygen
h2: V
o2=1:0.5 – 5, preferably volume ratio is V
h2: V
o2=1:1 – 2; The air speed of oxidative dehydrogenation is 1000 – 15000h
-1, preferably air speed is 5000 – 12000h
-1, reaction temperature is 100 – 170 DEG C, and preferably temperature is 130 – 140 DEG C, and reaction pressure is 0.1 – 3.0MPa, and preferably pressure is 0.5 – 1.0MPa.
Beneficial effect of the present invention: compared with prior art, the PdO/Al prepared by the present invention
2o
3catalyst has high strength and anti abrasive characteristic, this catalyst is exclusively used in the CO oxidative dehydrogenation of fluidized-bed reactor, solve current fixed bed oxidative dehydrogenation reactor and move heat difficulty, reactor volume amplifies limited technological deficiency, feed gas containing carbon monoxide of the present invention passes through catalyst and the reaction process of fluid bed oxidative dehydrogenation, improve stability and the reaction velocity of catalyst, effectively can solve the industrial scale-up problem of coal-ethylene glycol technology Raw gas CO oxidative dehydrogenation process.
Accompanying drawing explanation
Fig. 1 is fluidized bed plant schematic diagram, wherein, 101 is reaction gas inlet, and 102 is gas distributor, and 103 is riser and reaction zone, 104 is cyclone separator, 105 for reaction after gas vent, 106 be filter, 107 be down-comer I section, 108 be decaying catalyst export, 109 is down-comer II section, and 110 is fresh catalyst and regenerated catalyst entrance.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
In fluidized bed plant as shown in Figure 1, carry out CO oxidative dehydrogenation process flow process is: first replace with the gas in nitrogen fluid bedreactors, preheating catalyst, by CO unstripped gas and and O
2enter gas distributor (102) by proportional quantity fully to mix, after preheating, agitate the PdO/Al of preheating
2o
3catalyst carries out oxidative dehydrogenation to riser region (103), gas solid separation is realized at cyclone separator (104) after reaction, gas goes out reactor through filter (106) by gas vent (105), solid enters down-comer (107), the catalyst that (108) discharge inactivation is exported, by fresh catalyst and regenerated catalyst entrance (110) make-up catalyst in down-comer region by the decaying catalyst in down-comer region.
Embodiment 1:
Vehicle element: spherical alumina support (for what customize from one, Shandong alumina producer by parameter request) cools after Muffle furnace 700 DEG C of roasting 12h, and after tested, specific area is 286m
2/ g, average diameter is 0.72mm, and bulk density is 0.80g/ml, and Mass Loss is about 0.1%, and compression strength is about 80N/.
Pd mass percentage is the catalyst P dO/Al of 0.5%
2o
3preparation: adopt equi-volume impregnating, according to stoichiometry, palladium nitrate is dissolved in the dilute nitric acid solution of 1%, the mass percentage of Pd in solution is made to be 0.5%, isopyknic spherical alumina support is immersed dipping solution, put into baking oven after dipping 8h and dry 8h at 150 DEG C, put into Muffle furnace again at 450 DEG C of roasting 12h, obtained required PdO/Al
2o
3catalyst.
In device as shown in Figure 1, carry out application experiment with this catalyst, wherein the riser diameter of fluidized-bed reactor be 80mm, highly for 1200mm; Carry out preheating to catalyst after completing displacement with the gas in nitrogen fluid bedreactors, preheater temperature controls at 110 DEG C, passes into CO unstripped gas (H
2volume content is 1.5%) and metering O
2(V
h2: V
o2=1:1.5) enter preheater, preheater temperature controls at 110 DEG C, and the total air speed of gas is 5000h
-1, reaction pressure is 0.5MPa, and reacting gas agitates catalyst to react to riser region, and riser chuck control temperature is at 130 DEG C, and reaction temperature is 134 DEG C, reacted gas through gas-chromatography on-line monitoring, H
2content is 25ppm.
Embodiment 2:
Vehicle element and method for preparing catalyst are with embodiment 1, and the Pd mass percentage unlike catalyst is 1%.
Take a certain amount of PdO/Al
2o
3put into that diameter is 80mm, riser height is the fluidized-bed reactor of 1200mm, carry out preheating to catalyst after completing displacement with the gas in nitrogen fluid bedreactors, preheater temperature controls at 100 DEG C, passes into CO unstripped gas (H
2volume content is 4.0%) and metering O
2(V
h2: V
o2=1:2.5) enter preheater, preheater temperature controls at 110 DEG C, and the total air speed of gas is 8000h
-1, reaction pressure is 1.0MPa, reacting gas drive catalyst react to riser region, riser chuck control temperature is at 125 DEG C, and reaction temperature is 139 DEG C, reacted gas through gas-chromatography on-line monitoring, H
2content is 44ppm.
Embodiment 3:
Vehicle element and catalyst method are with embodiment 1, and the Pd mass percentage unlike catalyst is 2%.
Take a certain amount of PdO/Al
2o
3put into that diameter is 80mm, riser height is the fluidized-bed reactor of 1200mm, carry out preheating to catalyst after completing displacement with the gas in nitrogen fluid bedreactors, preheater temperature controls at 100 DEG C, passes into CO unstripped gas (H
2volume content is 1.5%) and metering O
2(V
h2: V
o2=1:3) enter preheater, preheater temperature controls at 110 DEG C, and the total air speed of gas is 12000h
-1, reaction pressure is 1.5MPa, reacting gas drive catalyst react to riser region, riser chuck control temperature is at 120 DEG C, and reaction temperature is 137 DEG C, reacted gas through gas-chromatography on-line monitoring, H
2content is 28ppm.
Embodiment 4:
Vehicle element and catalyst method are with embodiment 1, and the Pd mass percentage unlike catalyst is 0.2%.
Take a certain amount of PdO/Al
2o
3put into that diameter is 80mm, riser height is the fluidized-bed reactor of 1200mm, carry out preheating to catalyst after completing displacement with the gas in nitrogen fluid bedreactors, preheater temperature controls at 120 DEG C, passes into CO unstripped gas (H
2volume content is 1.5%) and metering O
2(V
h2: V
o2=1:2) enter preheater, preheater temperature controls at 120 DEG C, and the total air speed of gas is 9000h
-1, reaction pressure is 3MPa, reacting gas drive catalyst react to riser region, riser chuck control temperature is at 130 DEG C, and reaction temperature is 132 DEG C, reacted gas through gas-chromatography on-line monitoring, H
2content is 15ppm.
Claims (6)
1. a CO dehydrogenation fluidized-bed reaction catalyst, its chemical formula is PdO/Al
2o
3, wherein PdO is active component, and the mass percentage that Pd accounts for catalyst is 0.05 – 3.0%; Al
2o
3for the carrier of catalyst, the spheric granules of to be diameter be 0.5 – 2.5mm, its specific area is 200 – 400m
2/ g, bulk density is 0.5 – 0.9g/ml, compression strength>=50N/, Mass Loss≤0.4%.
2. CO dehydrogenation fluidized-bed reaction catalyst according to claim 1, is characterized in that the mass percentage of Pd in catalyst is 0.2 – 0.5%; Al
2o
3the diameter of carrier is 0.8 – 1.0mm, and specific area is 250 – 300m
2/ g, bulk density is 0.7 – 0.8g/ml, and compression strength is 80 – 120N/, and Mass Loss is 0.05 – 0.1%.
3. prepare a method for CO dehydrogenation fluidized-bed reaction catalyst according to claim 1, concrete steps are as follows:
Soluble palladium salt is dissolved in diluted acid and prepares dipping solution, then by etc. the Al of body
2o
3dipping wherein; In dipping solution, the consumption of palladium salt is that 0.05 – 3.0% determines, by carrier A l by carrying Pd mass percentage in palladium rear catalyst
2o
3being immersed in dipping solution makes palladium salt fully be impregnated on carrier, leaches, in 100 –, 200 DEG C of dryings, after drying in Muffle furnace in air atmosphere in 350 –, 600 DEG C of roasting 8 – 24h, obtain PdO/Al
2o
3catalyst;
Described soluble palladium salt is the one in palladium nitrate, palladium, palladium acetylacetonate, palladium bromide, palladium bichloride; One in the hydrochloric acid of described diluted acid to be concentration be 0.05 – 0.1M, nitric acid, sulfuric acid, acetic acid, hydrobromic acid.
4. the preparation method of CO dehydrogenation fluidized-bed reaction catalyst according to claim 3, is characterized in that the consumption of palladium salt in dipping solution is that 0.2 – 0.5% determines by carrying Pd mass percentage in palladium rear catalyst; The load Al of palladium salt
2o
3the baking temperature of carrier is 130 – 160 DEG C; Sintering temperature is 450 – 500 DEG C.
5. an application for CO dehydrogenation fluidized-bed reaction catalyst, its processing step is: by the O of feed gas containing carbon monoxide and metering
2enter gas distributor fully mix laggard enter fluidized-bed reactor, agitate PdO/Al
2o
3catalyst carries out oxidative dehydrogenation to riser, and reacted material enters cyclone separator and is separated, and gas-phase product goes out reaction tube from gas vent, dust and a small amount of PdO/Al
2o
3catalyst enters down-comer, can a small amount of H in feed gas containing carbon monoxide after reaction
2be removed to below 50ppm; Catalyst after inactivation is discharged from exit, down-comer lower end, and fresh catalyst and regenerated catalyst supplement from down-comer lower inlet; In described feed gas containing carbon monoxide, CO volumn concentration is 50 – 99.5%, H
2volumn concentration is 0.1 – 10%, and the amount of oxygen wherein added is V according to the volume ratio of hydrogen and oxygen
h2: V
o2=1:0.5 – 5, the air speed of oxidative dehydrogenation is 1000 – 15000h
-1, reaction temperature is 100 – 170 DEG C, and reaction pressure is 0.1 – 3.0MPa.
6. the application of CO dehydrogenation fluidized-bed reaction catalyst according to claim 5, is characterized in that in described feed gas containing carbon monoxide, CO volumn concentration is 96 – 99.5%, H
2volumn concentration is 0.5 – 4%, and the amount of oxygen wherein added is V according to the volume ratio of hydrogen and oxygen
h2: V
o2=1:1 – 2; The air speed of described oxidative dehydrogenation is 5000 – 12000h
-1, reaction temperature is 130 – 140 DEG C, and pressure is 0.5 – 1.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410327115.1A CN104667912A (en) | 2014-07-10 | 2014-07-10 | Catalyst for CO dehydrogenation fluidized bed reaction and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410327115.1A CN104667912A (en) | 2014-07-10 | 2014-07-10 | Catalyst for CO dehydrogenation fluidized bed reaction and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104667912A true CN104667912A (en) | 2015-06-03 |
Family
ID=53303811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410327115.1A Pending CN104667912A (en) | 2014-07-10 | 2014-07-10 | Catalyst for CO dehydrogenation fluidized bed reaction and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104667912A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080538A (en) * | 2015-06-26 | 2015-11-25 | 中国科学院福建物质结构研究所 | Catalyst for purifying and dehydrogenating CO raw material gas and preparation method for catalyst |
| CN105617953A (en) * | 2016-01-08 | 2016-06-01 | 浙江大学 | Circulating fluidized bed with semi-conical descending section |
| CN107308962A (en) * | 2017-06-13 | 2017-11-03 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenations purification Pd Cl/CeOCl catalyst and preparation method |
| CN107497425A (en) * | 2017-07-05 | 2017-12-22 | 中国科学院福建物质结构研究所 | Two-part fluid bed CO dehydrogenations purify reaction technology and used catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080262281A1 (en) * | 2004-03-29 | 2008-10-23 | Basf Aktiengesellschaft | Catalyst Used for the Oxidation of Hydrogen, and Method for the Dehydrogenation of Hydrocarbons |
| CN102649557A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Oxidative dehydrogenation method for raw material containing CO gas |
| CN102649055A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for oxidative dehydrogenation of raw materials containing CO (carbon monoxide) gas |
| CN102649559A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for CO gas raw material dehydrogenation through catalytic oxidation reaction |
| CN102649552A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | CO gas oxydehydrogenation method |
-
2014
- 2014-07-10 CN CN201410327115.1A patent/CN104667912A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080262281A1 (en) * | 2004-03-29 | 2008-10-23 | Basf Aktiengesellschaft | Catalyst Used for the Oxidation of Hydrogen, and Method for the Dehydrogenation of Hydrocarbons |
| CN102649557A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Oxidative dehydrogenation method for raw material containing CO gas |
| CN102649055A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for oxidative dehydrogenation of raw materials containing CO (carbon monoxide) gas |
| CN102649559A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for CO gas raw material dehydrogenation through catalytic oxidation reaction |
| CN102649552A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | CO gas oxydehydrogenation method |
Non-Patent Citations (1)
| Title |
|---|
| 强根荣等: "《化学工业出版社》", 31 August 2010 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080538A (en) * | 2015-06-26 | 2015-11-25 | 中国科学院福建物质结构研究所 | Catalyst for purifying and dehydrogenating CO raw material gas and preparation method for catalyst |
| CN105080538B (en) * | 2015-06-26 | 2018-07-20 | 中国科学院福建物质结构研究所 | A kind of CO raw material gas purifyings catalyst for dehydrogen and preparation method thereof |
| CN105617953A (en) * | 2016-01-08 | 2016-06-01 | 浙江大学 | Circulating fluidized bed with semi-conical descending section |
| CN107308962A (en) * | 2017-06-13 | 2017-11-03 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenations purification Pd Cl/CeOCl catalyst and preparation method |
| CN107497425A (en) * | 2017-07-05 | 2017-12-22 | 中国科学院福建物质结构研究所 | Two-part fluid bed CO dehydrogenations purify reaction technology and used catalyst |
| CN107497425B (en) * | 2017-07-05 | 2019-07-30 | 中国科学院福建物质结构研究所 | Two-part fluidized bed CO dehydrogenation purification reaction technology and used catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2643369C2 (en) | Method for production of unsaturated esters from aldehydes, by direct oxidative etherification | |
| CN102039143B (en) | Preparation method of catalyst for acrylic acid by oxidizing acraldehyde | |
| CN104667912A (en) | Catalyst for CO dehydrogenation fluidized bed reaction and preparation method and application thereof | |
| CN103373706B (en) | A kind of methane reforming hydrogen production process and device | |
| WO2008023851A1 (en) | Catalyst for producing hydrocarbon from synthetic gas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from synthetic gas | |
| CN106582650A (en) | Preparation method of Co particle coated CNT (carbon nanotube) catalytic material and application of catalytic material in cyclohexane oxidation reaction | |
| CN110548499A (en) | Composite carrier catalyst for acetylene hydrochlorination and application thereof | |
| CN109529821A (en) | A kind of palladium-based catalyst for thermocatalytic Degradation Formaldehyde | |
| CN106268858A (en) | The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation and preparation method and application | |
| CN107952495B (en) | Regeneration method and application of Fischer-Tropsch synthesis catalyst | |
| CN109569650A (en) | One kind is for CO coupling catalyst for synthesizing oxalic ester and preparation method thereof | |
| CN107311150A (en) | A kind of method that high efficiency continuously fluid bed prepares CNT | |
| CN108114729A (en) | A kind of anthraquinone hydrogenation catalyst and its preparation method and application | |
| CN103894221B (en) | A kind of method utilizing molecular sieve catalyst without mercury catalyzing acetylene preparing vinyl chloride by hydrochlorination | |
| CN107649134A (en) | A kind of method for preparing porous charcoal metal supported catalyst using coal or gasification of biomass | |
| CN102600912A (en) | Pretreatment method for improving performance of methane and carbon dioxide dry reforming catalyst | |
| CN105536790B (en) | A kind of catalyst for hydrogen production from methanol-steam reforming and preparation method thereof | |
| CN107790195B (en) | Reduction method of iron-based Fischer-Tropsch catalyst | |
| CN107497425B (en) | Two-part fluidized bed CO dehydrogenation purification reaction technology and used catalyst | |
| CN110721707B (en) | Low-temperature deoxidation catalyst for synthesis gas and preparation and application thereof | |
| CN107519914A (en) | A kind of molecular sieve catalyst for carbonylation and its preparation method and application | |
| JP2002030036A (en) | Method of producing vinyl acetate | |
| JP4604607B2 (en) | Catalyst regeneration method | |
| CN105732267A (en) | Selective hydrogenation method for C2 fraction | |
| Guo et al. | Highly dispersed Ag/SiO2 catalyst with weak metal-support interaction for diethyl oxalate hydrogenation to ethyl glycolate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171229 Address after: 562300 Guizhou Province, Xingren Buyi and Miao Autonomous Prefecture Xingren County Economic Development Zone (Industrial Park) Applicant after: Guizhou Xin alcohol science and Technology Development Co., Ltd. Address before: Yang Qiao Road, Gulou District of Fuzhou city of Fujian Province, No. 155 350002 Applicant before: Fujian Institute of Research on the Structure of Matter, Chinese Academy of Scie |
|
| TA01 | Transfer of patent application right | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150603 |
|
| WD01 | Invention patent application deemed withdrawn after publication |