CN101185895A - Catalyst for synthesizing low carbon mellow with synthesis gas and preparation method thereof - Google Patents
Catalyst for synthesizing low carbon mellow with synthesis gas and preparation method thereof Download PDFInfo
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- CN101185895A CN101185895A CNA2006100978698A CN200610097869A CN101185895A CN 101185895 A CN101185895 A CN 101185895A CN A2006100978698 A CNA2006100978698 A CN A2006100978698A CN 200610097869 A CN200610097869 A CN 200610097869A CN 101185895 A CN101185895 A CN 101185895A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 3
- 239000011787 zinc oxide Substances 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 238000000975 co-precipitation Methods 0.000 abstract description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 abstract 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 abstract 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002535 CuZn Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
The invention discloses a catalyst for synthesizing low carbon mixed alcohol with synthetic gas and a preparation method. The main components of the catalyst are copper oxide, zinc oxide, chromium oxide, alumina, and an appropriate amount of other assistants, which are expressed by the general formula Cu(Zn)a(Cr)b(Al)c(M)d(A)e(O)x; the catalyst is prepared by coprecipitation, and the assistant is added by impregnation. Under appropriate conditions, the catalyst can lead CO and hydrogen to react to produce a mixture of oxidation compounds which comprises methanol, ethanol, propanol, isobutanol, pentanol, and small amount of C5.
Description
Technical field:
The invention belongs to catalyst technical field, be specifically related to a kind of Catalysts and its preparation method that is used for synthesizing low-carbon alcohol from synthetic gas.
Background technology:
Since the seventies in 20th century, the mankind just recognize that energy development and environmental protection will become two great strategy themes of human society survival and development.Along with the mankind to the continuing to increase of mineral resources demand, the continuous consumption of natural resources, the earth can be supplied with human resource and also reduce thereupon, actively seeks and to develop new energy system very urgent concerning the mankind.In world's energy resource structure, oil only accounts for 6.6%, and coal will account for 78.9%.As coal producer the biggest in the world, the energy resource structure characteristics of the few oil of middle national wealth coal are more obvious.Can be easy to prepare CO and H by coal now
2, how to utilize CO and H
2The synthetic chemical products that can satisfy necessary for human become the human focus of paying close attention to, by CO catalytic hydrogenation synthesizing low-carbon mixed alcohol (C
1-C
5Mixed alcohol) be one of the important channel of coal resources clean utilization, MAS progressively shows especially in the using value of fuel and chemical field in recent years, and correlative study becomes increasingly active.
USP4,593,015, USP4,668,656 provide the catalyst of elements such as a kind of Cu of containing, Th and alkali metal, are used for the synthesis gas synthesizing low-carbon mixed alcohol, and methanol content is no more than 85% in its product, and all the other are the gasoline component that contains mixed alcohol.
USP 4,994, and 498 provide the MoS of elements such as a kind of Ta of containing and alkali metal
2Catalyst series is used for the synthesis gas synthesizing low-carbon mixed alcohol, and it becomes pure selectivity to be up to 80%, and pure space-time yield is up to 0.41.
USP5,096,688 provides a kind of Catalytic processes, adopts two sections to synthesize, and first section employing contains the base metal catalysts of Co, and second section employing contains the Cu-Cr catalyst.
CN1179993 provides a kind of rhodium base catalyst of low carbon alcohol by synthetic gas, and oxygenate overall selectivitys such as its methyl alcohol, ethanol, acetaldehyde, propyl alcohol reach more than 90%, wherein C
2The oxygenate selectivity is up to～86%.
CN1481934 provides a kind of ferromagnetic catalyst of cupric of low carbon alcohol by synthetic gas, its C
2 +The alcohol selectivity reaches 68%, and pure space-time yield is up to 1.25.CN1428192 provides a kind of Zr-Cu series catalysts, its CO conversion ratio, C
2 +Alcohol selectivity and pure space-time yield all reach higher level.
Above catalyst respectively has characteristics, when the CO conversion ratio is higher, and C
2 +The alcohol selectivity is low or water content is high, works as C
2 +The alcohol selectivity is when high, and the CO conversion ratio is lower, even also be uneconomic industrial being applied.Thereby catalyst constantly improved, to obtain high CO conversion ratio C simultaneously
2 +Alcohol selectivity and all higher catalyst of pure space-time yield are the emphasis that people study for a long time.
Summary of the invention:
The object of the present invention is to provide a kind of Catalysts and its preparation method that is used for synthesizing low-carbon alcohol from synthetic gas, this catalyst has higher CO conversion rate and higher C
2More than (C
2 +) pure selectivity.
Catalyst key component of the present invention is cupric oxide, zinc oxide, chromium oxide, aluminium oxide and other an amount of auxiliary agent, available general formula is expressed as Cu (Zn) a (Cr) b (Al) c (M) d (A) e (O) x, wherein M is one or more in the metallic elements such as V, Mo, Mn, Mg, Ce, and A is the alkali carbonate auxiliary agent; A is 0.5～2, and b is 0.1～0.4, and c is 0.05～0.35, and d is 0～0.2, and e is 0.02～0.9, and x satisfies the required atom number of each element valence.
Preferred M is V, Mn, Ce in the general formula; A is 0.9～1.3, and b is 0.2～0.35, and c is 0.25～0.35, and d is 0.1～0.2, and e is 0.02～0.40; Auxiliary agent A is a potash.
Catalyst of the present invention adopts the method for co-precipitation to be prepared, and the salt that is about to each metal component is wiring solution-forming in proportion, adopts precipitating reagent to precipitate then, and precipitating reagent is Na
2CO
3, NaHCO
3, NH
4HCO
3, (NH
4)
2CO
3Or a kind of in the ammoniacal liquor, precipitation temperature is 30 ℃～g0 ℃, the precipitation endpoint pH is 6.8～8.0, through aging, filtration, washing, oven dry, granulation, roasting, immersion auxiliary agent, roasting and compression molding operation are prepared from again.
The salt of metal component is generally nitrate; Auxiliary agent sprays into by wiring solution-forming; Sintering temperature in the preparation process is at 300 ℃～450 ℃.The catalyst that makes is diameter 3mm～6mm, the cylindrical tablet of height 3mm～8mm, and its specific surface is at 30m
2/ g～100m
2/ g.
The specific embodiment:
Catalyst of the present invention is implemented according to above step, is elaborated below by embodiment.
Embodiment 1
Press general formula Cu (Zn)
1.25(Cr)
0.38(Al)
0.38(M)
0(A) e (O) x.The chromium nitrate solution 100ml that gets aluminum nitrate solution 100ml, the 1.35M of 2.0M copper nitrate solution 178ml, 2.0M zinc nitrate solution 222ml, 1.35M is mixed with the 1000ml mixed solution, in having the stillpot of stirring, mixed solution and sodium carbonate liquor are carried out co-precipitation, the control precipitation temperature is at 75 ℃～80 ℃, the precipitation endpoint pH is 7.5, then at 80 ℃～85 ℃ aging 30min, through washing, oven dry, pulverizing, 320 ℃ of roastings, get 11.5gK again
2CO
3Be made into the 100ml aqueous solution, evenly sneak into above-mentioned base-material, drying again, 350 ℃ of roastings add suitable quantity of water and graphite, and last compressing tablet becomes cylindrical tablet, and the particle that is broken into 0.45mm～0.90mm more promptly gets available catalyst (K1)
Embodiment 2
Press general formula Cu (Zn)
0.75(Cr)
0.3(Al)
0.3(M)
0(A) e (O) x.The chromium nitrate solution 100ml that gets aluminum nitrate solution 100ml, the 1.35M of 2.0M copper nitrate solution 229ml, 2.0M zinc nitrate solution 171ml, 1.35M is mixed with the 1000ml mixed solution, in having the stillpot of stirring, mixed solution and sodium carbonate liquor are carried out co-precipitation, the control precipitation temperature is at 75 ℃～80 ℃, the precipitation endpoint pH is 7.5, then at 80 ℃～85 ℃ aging 30min, through washing, oven dry, pulverizing, 320 ℃ of roastings, get base-material again.Get 6.13gK
2CO
3Be made into the 100ml aqueous solution, evenly sneak into above-mentioned base-material, drying again, 350 ℃ of roastings add suitable quantity of water and graphite, and last compressing tablet becomes cylindrical tablet, and the particle that is broken into 0.45mm～0.90mm more promptly gets available catalyst (K2).
Embodiment 3
Press general formula Cu (Zn)
1.5(Cr)
0.65(Al)
0.65(M)
0.12(A) e (O) x.Get 2.0M copper nitrate solution 178ml, 2.0M zinc nitrate solution 266ml, Al (NO3) 39H2O86.5g, Ce (NO
3)
36H
2O11.6g, Cr (NO
3)
39H
2O92.3g, 50%Mn (NO
3)
3Solution 9.1g is mixed with the 1000ml mixed solution, in having the stillpot of stirring, mixed solution and sodium carbonate liquor are carried out co-precipitation, the control precipitation temperature is at 75 ℃～80 ℃, the precipitation endpoint pH is 7.5, then at 80 ℃～85 ℃ aging 30min, through washing, oven dry, pulverizing, 320 ℃ of roastings, get base-material again.Get 4.3gK
2CO
3Be made into the 100ml aqueous solution, evenly sneak into above-mentioned base-material, drying again, 350 ℃ of roastings add suitable quantity of water and graphite, and last compressing tablet becomes cylindrical tablet, and the particle that is broken into 0.45mm～0.90mm more promptly gets available catalyst (K3).
Embodiment 4
Press general formula CuZn (Cr)
0.33(Al)
0.33(M)
0.19(A) e (O) x.Get aluminum nitrate solution 225ml, the Ce (NO of 2.36M copper nitrate solution 240ml, 2.30M zinc nitrate solution 245ml, 0.85M
3)
36H
2O6.1g, Cr (NO
3)
39H
2O75.0g, 50%Mn (NO
3)
3Solution 9.1g is mixed with the 1000ml mixed solution, in having the stillpot of stirring, mixed solution and sodium carbonate liquor are carried out co-precipitation, the control precipitation temperature is at 75 ℃～80 ℃, the precipitation endpoint pH is 7.5, then at 80 ℃～85 ℃ aging 30min, through washing, oven dry, pulverizing, 320 ℃ of roastings, get base-material again.Get 6.6gK
2CO
3With 6.0gV
2O
5Be made into the 100ml aqueous solution, evenly sneak into above-mentioned 150g base-material, drying again, 350 ℃ of roastings add suitable quantity of water and graphite, and last compressing tablet becomes cylindrical tablet (K4), and the particle that is broken into 0.45mm～0.90mm more promptly gets available catalyst (K4-1).
Embodiment 1
With the catalyst 2ml that previous embodiment 1 makes, pack in Φ 10 * 2.0 tubular reactors, reduce with hydrogen, be 5.0Mpa～15.0Mpa at pressure then, temperature is under 250 ℃～400 ℃ conditions, feeds CO and H
2Gaseous mixture, gas space velocity are 3000h
-1～8000h
-1, reacted gas promptly gets the mixed alcohol product through condensation.Fluid product is analyzed through gas-chromatography, the results are shown in Table 1.
Product distributes under the table 1 catalyst K1 differential responses temperature
(P＝10.0MPa，H
2/CO＝3.1，GHSV＝6000h
-1)
Embodiment 2
The catalyst K2 that previous embodiment 2 is made detects by the condition of embodiment 1, the results are shown in Table 2.
Table 2 catalyst K2 product under the differential responses temperature distributes
(P＝10.0MPa，H
2/CO＝3.1，GHSV＝6000h
-1)
Embodiment 3
The catalyst that previous embodiment 3 is made is that 10.0MPa, temperature are 350 ℃, H by the method for embodiment 1 at pressure
2/ CO=1.6～2.2, GHSV=6000h
-1Detect under the condition, the results are shown in Table 3, table 4.
Table 3K3 catalyst alcohol product distributes
Table 4K3 catalyst performance index
Embodiment 4
The method that the catalyst (K4-1) that previous embodiment 4 is made is pressed embodiment 1 is that 10.0MPa, temperature are 350 ℃, GHSV=6000h at pressure
-1Detect different H under the condition
2/ CO testing result sees Table 5.
Table 5K4-1 catalyst is at different H
2Pure product distributes under/CO the condition
Embodiment 5
The method that the catalyst (K4-1) that previous embodiment 4 is made is pressed embodiment 1 is that 10.0MPa, temperature are 350 ℃, H at pressure
2Detect under/CO=1.2 the condition, different GHSV testing results see Table 6.
Table 6K4-1 catalyst pure product under different GHSV conditions distributes
Claims (10)
1. a catalyst that is used for synthesizing low-carbon alcohol from synthetic gas is characterized in that this catalyst key component is cupric oxide, zinc oxide, chromium oxide, aluminium oxide and auxiliary agent, general formula Cu (Zn)
a(Cr)
b(Al)
c(M)
d(A)
e(O)
x, wherein M is one or more in V, Mo, Mn, Mg, the Ce metallic element, A is the alkali carbonate auxiliary agent; A is 0.5～2, and b is 0.1～0.4, and c is 0.05～0.35, and d is 0～0.2, and e is 0.02～0.9, and x satisfies the required atom number of each element valence.
2. catalyst according to claim 1 is characterized in that the M in the general formula is V, Mn, Ce.
3. catalyst according to claim 1 is characterized in that a is 0.9～1.3 in the general formula, and b is 0.2～0.35, and c is 0.25～0.35, and d is 0.1～0.2, and e is 0.02～0.40.
4. catalyst according to claim 1 is characterized in that auxiliary agent A is a potash in the general formula.
5. one kind prepares Preparation of catalysts method according to claim 1, it is characterized in that by the preparation of following preparation process: with the salt of each metal component wiring solution-forming in proportion, adopt precipitating reagent to precipitate then, precipitating reagent is Na
2CO
3, NaHCO
3NH
4HCO
3, (NH
4)
2CO
3Or a kind of in the ammoniacal liquor, precipitation temperature is 30 ℃～80 ℃, the precipitation endpoint pH is 6.8～8.0, through aging, filtration, washing, oven dry, granulation, roasting, immersion auxiliary agent, roasting and compression molding operation are prepared from again.
6. as Preparation of catalysts method as described in the claim 5, it is characterized in that the catalyst that makes is diameter 3mm～6mm, the cylindrical tablet of height 3mm～8mm.
7. as Preparation of catalysts method as described in the claim 5, the salt that it is characterized in that metal component is nitrate.
8. as Preparation of catalysts method as described in the claim 5, it is characterized in that auxiliary agent sprays into by wiring solution-forming.
9. as Preparation of catalysts method as described in the claim 5, it is characterized in that sintering temperature in the preparation process is at 300 ℃～450 ℃.
10. as Preparation of catalysts method as described in the claim 5, its specific surface of catalyst that it is characterized in that making is at 30m
2/ g～100m
2/ g.
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|---|---|---|---|
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| CN100584456C CN100584456C (en) | 2010-01-27 |
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ID=39478641
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653729B (en) * | 2008-08-20 | 2011-11-02 | 青岛生物能源与过程研究所 | Catalyst used for preparing lower alcohol by synthesis gas, preparation method and application thereof |
| CN102531819A (en) * | 2010-12-30 | 2012-07-04 | 中国科学院大连化学物理研究所 | Method for preparing methane and methanol by using synthesis gas |
| RU2455068C2 (en) * | 2010-08-30 | 2012-07-10 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Catalyst, preparation method thereof and method of producing synthetic gas from synthetic hydrocarbon fuel |
| CN102872881A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Copper-based catalyst used in process of synthesizing low carbon mixed alcohol and preparation method and application of catalyst |
| CN102924368A (en) * | 2012-11-14 | 2013-02-13 | 连云港阳方催化科技有限公司 | Method of synthesis of 2-picoline through 5-ketohexanenitrile |
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