CN108250021A - Hydrogenation alkyne removal method for ethylene material in methanol-to-olefin process - Google Patents
Hydrogenation alkyne removal method for ethylene material in methanol-to-olefin process Download PDFInfo
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- CN108250021A CN108250021A CN201611245821.7A CN201611245821A CN108250021A CN 108250021 A CN108250021 A CN 108250021A CN 201611245821 A CN201611245821 A CN 201611245821A CN 108250021 A CN108250021 A CN 108250021A
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- Prior art keywords
- catalyst
- temperature
- carrier
- ethylene
- hydrogenation
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- 238000000034 method Methods 0.000 title claims abstract description 67
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 58
- 239000005977 Ethylene Substances 0.000 title claims abstract description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 14
- 150000001345 alkine derivatives Chemical class 0.000 title abstract description 19
- 230000008569 process Effects 0.000 title abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 171
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 44
- 229910017061 Fe Co Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 69
- 239000001257 hydrogen Substances 0.000 claims description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 46
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- 238000001354 calcination Methods 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000002803 maceration Methods 0.000 claims description 10
- -1 magnesia compound Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
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- 230000000694 effects Effects 0.000 abstract description 17
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- 238000001994 activation Methods 0.000 description 17
- 230000004913 activation Effects 0.000 description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 14
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
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- WZGWWPARMFQTAY-UHFFFAOYSA-N ethene;methanol Chemical group OC.C=C WZGWWPARMFQTAY-UHFFFAOYSA-N 0.000 description 5
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- 229910000859 α-Fe Inorganic materials 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 4
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- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
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- 238000005336 cracking Methods 0.000 description 4
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- 230000018109 developmental process Effects 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910021329 Fe4Al13 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
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- 230000008018 melting Effects 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 230000008929 regeneration Effects 0.000 description 2
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- 229910052707 ruthenium Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021007 Co2Al5 Inorganic materials 0.000 description 1
- 229910021214 Co2Al9 Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229910019108 CoAl3 Inorganic materials 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
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- 229910017372 Fe3Al Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910015370 FeAl2 Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
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- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 239000000306 component Substances 0.000 description 1
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- 239000011147 inorganic material Substances 0.000 description 1
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- 238000006384 oligomerization reaction Methods 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
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Abstract
A hydrogenation and alkyne removal method for ethylene materials in a methanol-to-olefin process uses a Fe-Co hydrogenation catalyst, and adds a methanol-to-ethylene product into a hydrogenation reactor for selective hydrogenation refining, wherein the hydrogenation object is trace acetylene contained in tower top effluent after the methanol-to-ethylene product is subjected to alkali washing → drying → demethanization → deethanization, and the raw material composition mainly comprises the following components: not less than 99.9% (phi) of ethylene, 5-100 ppm of acetylene and 1-10 ppm of CO. The reaction conditions are as follows: the inlet temperature of the reactor is 30-80 ℃, the reaction pressure is 1.5-3.0 MPa, and the airspeed is 2000-10000 h‑1(ii) a The hydrogenation catalyst is a Fe-Co selective hydrogenation catalyst, the carrier is a high-temperature-resistant inorganic oxide, the active components at least contain Fe and Co, and the catalyst contains 2-6% of Fe and 0.5-1.5% of Co by the mass of 100% of the catalyst; the specific surface of the catalyst is 10-200 m2The pore volume is 0.2 to 0.63 ml/g. The catalyst has mild hydrogenation activity and excellent ethylene selectivity, no ethylene loss, low green oil generation amount and low catalyst cost far lower than that of noble metal Pd catalyst.
Description
Technical field
The present invention relates to a kind of acetylene hydrogenation methods of ethylene product in preparing light olefins from methanol, and particularly one kind is in methanol
In the product of ethylene processed, the process for selective hydrogenation of trace acetylene is carried out using Fe-Co hydrogenation catalysts.
Background technology
The low-carbon alkenes such as ethylene, propylene are important basic chemical raw materials, with the development of Chinese national economy, particularly
Demand of the development of modern chemical industry to low-carbon alkene increasingly rises, and imbalance between supply and demand will also become increasingly conspicuous.So far, it produces
The important channel of the low-carbon alkenes such as ethylene, propylene, be still by naphtha, light diesel fuel (being all from oil) catalytic cracking,
Cracking, the raw material resources such as naphtha, light diesel fuel as ethylene production raw material are faced with increasingly severe short office
Face.In addition, crude oil in China import volume has accounted for half or so of processing total amount in recent years, using ethylene, propylene as raw material polyolefin
Product will maintain the quite high percentage of import.Therefore, development non-oil resource carrys out the technologies of preparing low-carbon olefins and increasingly causes
The attention of people.
The MTP techniques of methanol ethylene, the MTO techniques of propylene and preparing propylene from methanol are Chemical Engineering Technologies important at present.It should
The methanol that technology is synthesized using coal or natural gas produces low-carbon alkene as raw material, is development non-oil resource production ethylene, propylene etc.
The core technology of product.
MTO technology is the committed step in coal-to-olefin industrial chain, and technological process is predominantly suitably being grasped
Under the conditions of work, using methanol as raw material, suitable catalyst is chosen, by methanol dewatered in fixed bed and fluidized-bed reactor
Low-carbon alkene.According to the difference of purpose product, MTO technology is divided into methanol ethylene, propylene, preparing propylene from methanol.Methanol
Entirely reaction can be divided into two stages to alkene processed：Water smoking, cracking reaction stage
1. the water smoking
2CH3OH→CH3OCH3+H2O+Q
2. the cracking reaction stage
The reaction process is mainly that the catalysis that dehydration reaction product dimethyl ether and a small amount of unconverted material benzenemethanol carry out is split
Solution reaction, including：
Main reaction (generation alkene)：
nCH3OH→CnH2n+nH2O+Q
nCH3OH→2CnH2n+nH2O+Q
N=2 and 3 (main), 4,5 and 6 (secondary)
Any of the above olefin product is gaseous state.
Side reaction (generation alkane, aromatic hydrocarbons, oxycarbide and coking)：
(n+1)CH3OH→CnH2n+2+C+(n+1)H2O+Q
(2n+1)CH3OH→2CnH2n+2+CO+2nH2O+Q
(3n+1)CH3OH→3CnH2n+2+CO2+(3n-1)H2O+Q
N=1,2,3,4,5 ... ...
nCH3OCH3→CnH2n-6+3H2+nH2O+Q
N=6,7,8 ... ...
Methanol is after being dehydrated, cracking, detach, the still second containing 5~100ppm in the ethylene feed of deethanizer overhead
Alkynes, it influences the polymerization process of ethylene, and product quality is caused to decline, and needs by the way that method of hydrotreating is selected to be removed.Ethylene
The selection of trace acetylene plus hydrogen have extremely important influence to the polymerization process of ethylene in material, in addition to ensureing to add hydrogen with enough
Activity, have under conditions of low acetylene content good except alkynes performance, ensure that the acetylene content of reactor outlet is up to standard, instead
Answer the hydrogen content that device exports up to standard outer, the selectivity for also requiring catalyst is excellent, can make the generation second that ethylene is as few as possible
Alkane, it is ensured that hydrogenation process does not bring the loss of device ethylene.
The selection of trace acetylene adds hydrogen mainly to use single hop reactor process in methanol-to-olefins device ethylene feed at present.
Reactor inlet material forms：Ethylene >=99.99% (Φ), 5~100ppm of acetylene, CO1~10ppm, hydrogen is using distribution
Mode, H2/C2H2=2~6.1.5~2.5MPa of reaction pressure, 2000~10000h of air speed-1, 25 DEG C~60 DEG C of inlet temperature.
Alkynes and diolefin hydrogenate catalyst are by the way that noble metal such as palladium is supported on porous Inorganic material carrier
On obtained (US4762956).In order to increase the selectivity of catalyst, the green oil that oligomerization generates when reducing by adding hydrogen is led
The catalyst inactivation of cause, the prior art employ the method for adding that such as group ib element is co-catalysis component in the catalyst：
Pd-Au (US4490481), Pd-Ag (US4404124), Pd-Co (US3912789) add in alkali or alkaline earth metal
(US5488024) etc., carrier used has aluminium oxide, silica (US5856262), loyal green stone of honeycomb (CN1176291) etc..
Patent US4404124 is prepared for the selective hydrogenation catalyst of active component palladium shell distribution by step impregnation method,
Can be applied to carbon two, the selection of C3 fraction adds hydrogen, to eliminate the propine allene in acetylene and propylene in ethylene.
US5587348 adjusts co-catalyst silver and is acted on palladium using aluminium oxide as carrier, adds in alkali metal, the fluorine of chemical bonding is prepared for
The C2 hydrogenation catalyst of function admirable.The catalyst, which has, reduces green oil generation, improves ethylene selectivity, reduces oxygen-containing chemical combination
The characteristics of object production quantity.US5519566 discloses a kind of method that wet reducing prepares silver and palladium catalyst, by maceration extract
Middle addition organic or inorganic reducing agent, prepares silver and palladium bi-component selective hydrogenation catalyst.
US5856262 is reported using the modified silica of potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) as carrier,
The method for preparing low in acidity palladium catalyst, in air speed 3000h-1, 35 DEG C of inlet temperature, entrance acetylene molar fraction 0.71%, hydrogen
Under conditions of alkynes molar ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Patent
Using aluminium oxide as carrier, addition co-catalyst silver acts on US4404124 with palladium, is prepared for the C2 hydrogenation catalysis of function admirable
Agent.The catalyst, which has, reduces ethane production quantity, acetylene of the absorption on catalyst surface is inhibited to carry out partial hydrogenation dimerization anti-
Should, inhibit 1,3-butadiene generation, reduce green oil generation, the characteristics of improving ethylene selectivity, reduce oxygenatedchemicals production quantity,
It is applied widely in ethylene industry.However, above-mentioned catalyst is prepared using infusion process, limited by preparation method
System, metal dispersity is only 30% or so, and there is also many deficiencies for catalyst performance, still there is further improved necessity.
CN101745389A discloses a kind of egg-shell catalyst for preparation of ethylene through selective hydrogenation of acetylene, belongs to oil
(natural gas) chemical products synthesize and new catalytic material technical field, be related to it is a kind of to preparation of ethylene through selective hydrogenation of acetylene have it is excellent
The egg-shell catalyst of good catalytic performance.It is characterized in that with aluminium oxide (Al2O3) bead be carrier, using infusion process prepare activity
Component palladium is in the loaded catalyst of eggshell type distribution, and using Ag to eggshell type Pd/Al2O3Catalyst is modified.Pd is loaded
It is 1~5 to measure as 0.01~0.1wt%, Ag and Pd atomic ratio.The invention has the advantages that the one kind provided is used for second
Alkynes selects the egg-shell catalyst of Hydrogenation ethylene, can be under the conditions of high conversion of alkyne, especially in the acetylene close to 100%
During conversion ratio, high ethylene selectivity is realized.
Due to the use of precious metals pd as active component, catalyst is of high cost.Research and develop remarkable novel of cheap, performance
C2 hydrogenation catalyst system is always the target that field scientific research personnel makes great efforts.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst is by being selected from the first component of cobalt, gold, silver and selecting second of component group of nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium
Into in addition catalyst further includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound.It urges
Fluorite structure is formed after agent calcining, use or regeneration.Catalyst oxide total content 0.01~50%, preferably calcination temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With activity, the selectivity after regeneration.The technology be still with cobalt, gold, silver, palladium etc. for active component, nickel, platinum, palladium, iron, cobalt,
Ruthenium, rhodium etc., by the oxide modifying to carrier, improve the regenerability of catalyst as component is helped.
CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, and active component is 5~15% nickel oxide
With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide
One or several kinds, additionally include 1~10% auxiliary agent.The inventive technique is mainly used for second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, have good deep hydrogenation ability.The technology be mainly used for rich in CO and
The complete plus hydrogen of ethylene, propylene, butylene etc., is not suitable for alkynes, the selection of alkadienes adds hydrogen in the various industrial tail gas of hydrogen.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
The intermetallic compound is selected from by CoAl, CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、
FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13The group of composition.Wherein preferred Fe4Al13And o-Co4Al13.Change between the metal
Object is closed to be prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead
Temperature 473K is answered, after stablizing reaction 20h, o-Co4Al13Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%,
Fe4Al13Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions
Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And
And catalyst is prepared using heat melting method, condition is harsh.
In conclusion the selective hydrogenation of low-carbon alkynes and alkadienes, at present mainly using noble metal catalyst, for non-
Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this
Problem, the present invention provide a kind of novel Fe-Co hydrogenation catalysts and preparation method thereof.
Invention content
Present invention aims at provide a kind of acetylene hydrogenation method of MTO technology ethylene feed, particularly suitable use
It, will be contained in two material of carbon from deethanizer overhead using Fe-Co hydrogenation catalysts in preparing light olefins from methanol technique
Trace acetylene carry out selective hydrogenation, be fully converted to ethylene.
It is characterized in that methanol-to-olefins device product, by separation, two material of carbon from deethanizer overhead is passed through with hydrogen
Later, selection plus hydrogen are carried out into adiabatic reactor reactor, Fe-Co selective hydrogenation catalysts, carrier is housed in adiabatic reactor reactor
For high-temperature inorganic oxide, for active component at least containing Fe, Co, catalyst contains Fe 2~8%, excellent containing Co 0.5~1.5%
Content is selected as Fe 3~5%, Co0.7~1.2%；The specific surface of catalyst is 10~200m2/ g, preferably 30~150m2/ g, hole
Hold for 0.2~0.63ml/g, preferably 0.3~0.55ml/g；Wherein catalyst be by impregnation method by active component load in
Fired on carrier, hydrogen atmosphere reduction is made；Reaction condition：30~80 DEG C of reactor inlet temperature, reaction pressure 1.5~
3.0MPa, 2000~10000h of air speed-1, hydrogen added in using distribution mode, and hydrogen/acetylene volume ratio is 2~20.
It is of the present invention to remove alkynes method, hydrogenation catalyst is used, carrier is high-temperature inorganic oxide, is such as aoxidized
One or more of aluminium, silica, zirconium oxide, magnesia etc..It is preferred that aluminium oxide or alumina series carrier, alumina series
Carrier refers to the complex carrier of aluminium oxide and other oxides, and wherein aluminium oxide accounts for more than the 50% of carrier quality, such as can be
The compound of the oxides such as aluminium oxide and silica, zirconium oxide, magnesia, preferably alumina-zirconia composite carrier, wherein
Alumina content is more than 60%.Aluminium oxide can be θ, α, γ type or the mixture of its a variety of crystal form, preferably α-Al2O3Or
- the Al containing α2O3Mixing crystal form aluminium oxide.
The present invention uses the preparation process of Fe-Co selective hydrogenation catalysts to include except alkynes method：
Catalyst is aged by preparing Fe predecessors aqueous solution, Co predecessor aqueous solutions, difference impregnated carrier, is dry respectively
Dry, roasting or with its mixed solution impregnated carrier, obtains after rear ageing, dry, roasting.
The present invention use hydrogenation catalyst preparation condition for：
30~60 DEG C, 10~60min of dip time of dipping temperature, maceration extract pH value 1.5~5.0；Aging Temperature 20~60
DEG C, 30~120min of digestion time；300~600 DEG C of calcination temperature, 240~300min of roasting time.Calcination temperature preferably 400
~500 DEG C.
Dry in the present invention is preferably temperature programming drying, and drying temperature program setting is：
Roasting is activation process in the present invention, and preferably temperature-programmed calcination, calcination temperature program setting is：
Incipient impregnation may be used in heretofore described catalyst, excessive dipping, surface spray, vacuum impregnation and repeatedly
It is prepared by any one impregnation method in infusion process.
It is as follows：
(1) carrier is weighed after measuring carrier water absorption rate.
(2) a certain amount of Fe predecessors (recommending soluble nitrate, chloride or sulfate) are accurately weighed by load capacity,
According to carrier water absorption rate and dipping method, dipping solution is prepared, and adjust maceration extract pH value 1.5~5.0 as required, and by solution
Be heated to 30~60 DEG C it is spare.
(3) using incipient impregnation or when spraying method, the carrier weighed can be put into rotary drum, adjusts rotary drum rotating speed
25~30 turns/min, carrier is totally turned over, prepared 30~60 DEG C of maceration extract is poured into or sprayed with given pace
It is spread across on carrier, loads 5~10min.
During using excessive infusion process, the carrier weighed is placed in container, then adds in 30~60 DEG C of dipping of preparation
Solution, the visibly moved device of Quick shaking, discharges rapidly the heat released in adsorption process, and makes active component uniform load to carrier
On, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.
During using vacuum impregnation technology, the carrier weighed is placed in cyclonic evaporator, is vacuumized, add in 30~60 DEG C
Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.
(4) catalyst impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution extra after dipping is filtered out, is then dried in an oven using the method for temperature programming, it is dry
Temperature program(me)：
(6) dried catalyst using temperature programming method is roasted, roasts temperature program：
Catalyst Co components are loaded using above-mentioned same steps, 300~600 DEG C of calcination temperature, preferably 400~
500 DEG C, two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
It can also contain other active components in addition to containing Fe, Co in catalyst composition in the present invention.
The catalyst of the present invention needs to be restored with hydrogen-containing gas, H2Content is preferably 10~50%, and reduction temperature 200~
350 DEG C, 240~360min of recovery time, 60~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；Optimum condition be
It is restored at 250~335 DEG C, 200~400h of volume space velocity-1, reduction pressure is preferably 0.1~0.5MPa.
Fe elements can be with Fe, Fe in catalyst of the present invention2O3、Fe3O4, several forms exist in FeO, preferably mainly
With α-Fe2O3Form exist, more preferably also contain a certain amount of Fe3O4.Recommend in the present invention in iron-containing activity composition at least
Co is added, and preferably Co mainly exists in the form of CoO, be conducive to formation, the dispersion of catalyst activity phase, and be conducive to
The stabilization of active phase improves catalyst activity, selectivity and anticoking capability.
Fe, Co and its different oxide relative amounts, pass through XRD diffraction peak areas integration method meters in catalyst of the present invention
It calculates.
The activation temperature of catalyst and activity composition, content and carrier related, the activated mistake of catalyst in the present invention
α-Fe are formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be excessively high；On the other hand, activation degree is again
It determines the reducing condition of catalyst, is provided in the catalyst used still with α-Fe in the present invention2O3The Fe of form for mainly into
Point, over reduction can influence the effect of catalyst instead, reduce activity, selectivity, easy coking.
It is of the present invention except alkynes method, add hydrogen object for methanol ethylene product through alkali cleaning → drying → demethanation → take off
After ethane separation, deethanizer overhead stream goes out trace acetylene contained in object, and specifically, raw material composition is mainly：Ethylene >=
1~10ppm of 99.9 volume %, acetylene 5~100ppm, CO.
In the present invention, hydrogenation material is reacted in single stage adiabatic bed reactor, will under Fe-Co catalyst actions
Contained trace acetylene selective hydrogenation, is converted into ethylene in material.
Of the present invention to remove alkynes method, reaction condition is：30~80 DEG C of reactor inlet temperature, reaction pressure 1.5~
3.0MPa, 2000~10000h of air speed-1。
Since hydrogen, the present invention plus hydrogen needed for hydrogen are not added in using distribution mode in material, hydrogen/acetylene volume ratio
It is 2~20.
Using the present invention except alkynes method, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene loss rate is low or even does not have
There is ethylene loss, " green oil " production quantity is far below noble metal catalyst, and catalyst anticoking capability is excellent, and using we
Method has preferable anti-N, S, As, O performance.
Description of the drawings
Attached drawing 1 is the C2 hydrogenation process flow chart using the methanol ethylene of sequence separation process.
1-reactor, 2-regenerator, 3-separator, 4-caustic wash tower, 5-drying tower, 6-domethanizing column, 7-de- second
Alkane tower, 8-ethylene separation tower, 9-propylene separation tower, 10-depropanizing tower, 11-ethylene finishing reactor.
Attached drawing 2 is using XRD spectra after 3 catalyst reduction of the embodiment of the present invention.
Attached drawing 3 is XRD spectra after 2 catalyst reduction of comparative example.
Attached drawing 4 is XRD spectra after 4 catalyst reduction of comparative example.
XRD determining condition：
German Brooker company D8ADVANCE X diffractometers
Tube voltage：40kV electric currents 40mA
Scanning：0.02 ° of step-length, 4 °~120 ° of frequency 0.5s scanning ranges, 25 DEG C of temperature
1 wavelength of Co K α, abscissa is 2 θ of the angle of diffraction in figure, and ordinate is diffracted intensity
Different crystal forms Fe oxide contents are obtained using XRD diffraction peak areas integration method in catalyst, and benchmark is metal oxygen
Compound total amount.
Symbol description in Fig. 2：
● it is α-Fe2O3, ■ Fe3O4, ▲ be CoO.
Symbol description in Fig. 3：
● it is α-Fe2O3, ■ Fe3O4, ☆ CoFe2O4。
Symbol description in Fig. 4：
■ is Fe3O4, ★ Fe,For Co.
Fig. 2 is XRD diffraction spectrograms, wherein α-Fe after catalyst reduction prepared by the method for the present invention2O3Relative amount
3.35%, there is Fe3O4Mutually occur, the second component exists in the form of CoO.
Fig. 3 is XRD diffraction spectrograms after comparative example catalyst reduction, and wherein Fe is mainly with α-Fe2O3Mutually exist, second group
Divide and combined to form CoFe with Fe2O4, there is Fe3O4Mutually occur.
Fig. 4 is XRD diffraction spectrograms after comparative example catalyst reduction, and wherein Fe is mainly with Fe3O4Mutually deposited with α-Fe mixed phases
The second component exists with simple substance Co phases.
Specific embodiment
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, give 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.
Analysis test method：
Specific surface：GB/T-5816
Kong Rong：GB/T-5816
Different crystal forms Fe oxide contents：XRD
Active component content：Atomic absorption method
Conversion ratio and selectivity are calculated by formula below in embodiment：
Conversion of alkyne (%)=100 × △ acetylene/entrance acetylene content
Ethylene selectivity (%)=100 × △ ethylene/△ acetylene
Embodiment 1
Weigh the trifolium-shaped alpha-alumina supports of 4.5 × 4.5mm of Φ.Appropriate ferric nitrate is taken, dissolves by heating and is gone in 60ml
In ionized water, pH value 2.5, maceration extract temperature 50 C are adjusted, incipient impregnation stirs rapidly carrier impregnation in carrier surface
6min, static 30min to adsorption equilibrium, 60 DEG C of ageing 30min, then in an oven according to program：Catalyst is dried, activation of catalyst is then carried out using programmed temperature method,
Activation procedure： Claim
Appropriate cobalt nitrate is taken, is impregnated according to above-mentioned preparation process.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst in reduction furnace with+60% nitrogen of 40% hydrogen before use, restored, 280 DEG C of reduction temperature, pressure
0.5MPa, recovery time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 10000h-1, pressure 1.5MPa, 40 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Embodiment 2
At 50 DEG C, by a certain amount of NaAlO2Solution and ZrCl4Solution is stirred, and is then neutralized with salpeter solution, stirring
10h, co-precipitation generate uniform Al-Zr particles.Product is filtered, Na therein is washed with deionized+And Cl-Ion, so
Add in afterwards appropriate mass concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C of dry 2h, 650 DEG C of roasting 4h
Obtain Zr-Al complex carriers.Aluminium oxide and zirconium oxide mass ratio are 4 in carrier:1.
Catalyst is prepared with alumina-zirconia composite carrier.Take appropriate iron chloride and cobalt chloride, dissolve by heating in go from
In sub- water, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, beaker dipping 10min is shaken, by extra leaching
Stain liquid filters out, and catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program：Catalyst is dried, activation of catalyst, activation are carried out using programmed temperature method
Program： Gained is urged
Agent physical index and each component content are shown in Table 1.
Catalyst in reduction furnace with+60% nitrogen of 30% hydrogen before use, restored, 300 DEG C of reduction temperature, pressure
0.5MPa, recovery time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 8000h-1, pressure 2.0MPa, 50 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 1.
Embodiment 3
Weigh the ball-type alpha-alumina supports 100ml of Φ 1.5mm.Appropriate ferric nitrate is taken to be dissolved in 40ml deionized waters, is adjusted
PH value 3.0,40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and 10min is loaded in rotary drum makes active component upload uniformly, bears
It carries process control to complete in 6min, then in an oven according to program：
Catalyst is dried, catalyst is moved into evaporating dish, activation of catalyst is carried out using programmed temperature method in Muffle furnace, activates journey
Sequence：Obtain a leaching
Catalyst.
Using first step same procedure, appropriate cobalt nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried,
Roasting, obtains final catalyst.Drying program： Calcination procedure： Gained catalyst object
Property index and each component content are shown in Table 1.
Catalyst in reduction furnace with 20% hydrogen before use, restored, 260 DEG C, pressure 0.5MPa of reduction temperature, also
Former time 4h.Restore rear catalyst XRD analysis as shown in Figure 2.
Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 6000h-1, pressure 2.5MPa, 40 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Embodiment 4
Ball-aluminium oxide-titanium dioxide carrier of the Φ 2.0mm weighed is placed in vacuum impregnation plant.Take a certain amount of ferric nitrate molten
It is spare to adjust pH value 3.5 in deionized water for solution.Vacuum impregnation plant vacuum pumping pump is opened, until vacuum degree 0.1mmHg, Ran Houcong
Charge door is slowly added to prepared maceration extract, and 5min is added, and catalyst surface mobile moisture is evaporated at 60 DEG C and is completely disappeared,
Complete load, the catalyst that will have been loaded, in an oven according to program：
Drying, in Muffle furnace according to：Roasting.
To a leaching catalyst.
Appropriate cobalt nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, roasts, obtains final catalyst.Drying program：Calcination procedure：
Gained catalyst physical index and each component content are shown in
Table 1.
Catalyst in reduction furnace with 15% hydrogen before use, restored, 320 DEG C, pressure 0.5MPa of reduction temperature, also
Former time 4h.Using hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 4000h-1, pressure 1.8MPa, 45 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Embodiment 5
The magnesia-silica complex carrier of 100ml Φ 4.0mm is weighed, is prepared and is catalyzed using 3 same procedure of embodiment
Agent, 550 DEG C of activation temperature.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 220 DEG C, pressure 0.5MPa of temperature, during reduction
Between 4h.During use by Catalyst packing in fixed-bed reactor.
Reaction condition：Air speed 3000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Embodiment 6
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using 3 same procedure of embodiment.Activation temperature
420℃.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 350 DEG C, pressure 0.5MPa of temperature, during reduction
Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 3000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Embodiment 7
The aluminium oxide of Φ 4.0mm is taken to make carrier, catalyst is prepared using 1 same procedure of embodiment, is lived at 480 DEG C
Change.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst in reduction furnace with 20% hydrogen before use, restored, 280 DEG C, pressure 0.5MPa of temperature, during activation
Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 8000h-1, pressure 2.5MPa, 50 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Comparative example 1
Take Φ 4.0mm alumina supports, specific surface 4.5m2/ g, Kong Rongwei 0.32ml/g.Using equi-volume impregnating,
By on a certain amount of silver nitrate solution incipient impregnation to carrier, ageing-drying-roasting obtains a leaching catalyst, then by one
Quantitative palladium bichloride dissolving, incipient impregnation, ageing-drying-roasting, obtaining final catalyst, (petrochemical industry research institute PAH-01 adds
Hydrogen catalyst).Catalyst Pd contents are that 0.050%, Ag contents are 0.20%.
Catalyst is at 100 DEG C with hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h-1.Added with attached drawing 1 Suo Shi
Hydrogen flow, Catalyst packing is in fixed-bed reactor.
Reaction condition and the results are shown in Table 2.
Comparative example 2
Carrier is made with Φ 4.0mm aluminium oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1
850℃.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 280 DEG C, pressure 0.5MPa of temperature, during activation
Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.Restore the XRD diffraction spectras of rear catalyst
Figure is as shown in Figure 3.
Reaction condition：Air speed 8000h-1, pressure 2.0MPa, 40 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Comparative example 3
The aluminium oxide for weighing Φ 4.0mm makees carrier, prepares catalyst using 1 same procedure of embodiment, lives at 450 DEG C
Change.Gained catalyst physical index and each component content are shown in Table 1.
Catalyst in reduction furnace with 45% hydrogen before use, restored, 300 DEG C, pressure 0.5MPa of temperature, during activation
Between 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 3000h-1, pressure 2.5MPa, 60 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Comparative example 4
Catalyst is prepared using the identical method of embodiment 1,450 DEG C activation after directly drive, catalyst before use,
It is restored in reduction furnace with 45% hydrogen, 300 DEG C, pressure 0.5MPa, soak time 4h of temperature.With attached drawing 1 Suo Shi plus hydrogen stream
Journey, Catalyst packing is in fixed-bed reactor.The XRD diffraction spectrograms for restoring rear catalyst are as shown in Figure 4.Gained catalyst
Physical index and each component content are shown in Table 1.
Reaction condition：Air speed 8000h-1, pressure 1.5MPa, 60 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
Comparative example 5
Catalyst is prepared using the identical method of embodiment 1, in 450 DEG C of activation.Gained catalyst physical index and each group
Point content is shown in Table 1.
Catalyst is restored in tube furnace, atmosphere be+55% nitrogen of 30% hydrogen, 450 DEG C of temperature, pressure
0.5MPa, soak time 4h.With hydrogen flow is added attached drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.
Reaction condition：Air speed 5000h-1, pressure 2.0MPa, 70 DEG C of reaction temperature.
Reaction condition and the results are shown in Table 2.
1 embodiment of table and comparative example carrier, catalyst physical index
2 embodiment of table and comparative example catalyst reaction performance
Note：Acetylene and ethylene gather and generate n-butene, further gather and generate " green oil ", are usually given birth in analysis with n-butene
Into scale sign catalyst green oil " production quantity.
To trace acetylene hydrogenation and removing contained in methanol ethylene product, need catalyst that there is good plus hydrogen to live
Property, meanwhile, higher is required selectivity, and traditional Pd-Ag hydrogenation catalysts ethylene loss is high, it is difficult to meet the requirement of the technique.
Using the C2 hydrogenation catalyst that Fe-Co is prepared as active component, industrialization Pd-Ag catalyst water is reached to the hydrogenation activity of alkynes
It is flat, meanwhile, Pd-Ag catalyst is significantly larger than to ethylene selectivity, ethylene does not lose, and " green oil " production quantity is far below noble metal
Catalyst.When Fe is mainly with α-Fe2O3In the presence of, while have a small amount of Fe3O4When, catalyst has good activity, without reduction
Or low-temperature reduction, Fe is all with α-Fe2O3In the presence of catalyst is without activity；There are α-Fe when restoring in transition, under catalyst activity
Drop, with the raising of Fe contents, certain raising trend is presented in catalyst activity, selectively can accordingly reduce.The addition of Co, has
Helping improve active component dispersion degree, catalyst activity improves, in the presence of helping component Co in the form of CoO, Fe and its oxide
Disperse best, calcination temperature is excessively high to form CoFe2O4, active component is agglomerated into larger particles, active to reduce, " green oil " generation
Amount raising.
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 deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of acetylene hydrogenation method of MTO technology ethylene feed, methanol-to-olefins device product comes by separation
It is passed through from two material of carbon of deethanizer overhead with after hydrogen, selection plus hydrogen is carried out into adiabatic reactor reactor, it is characterised in that：Absolutely
Equipped with Fe-Co selective hydrogenation catalysts in hott bed reactor, carrier is high-temperature inorganic oxide, and active component at least contains
Fe, Co, in terms of catalyst quality 100%, catalyst contains Fe 2~8%, containing Co 0.5~1.5%, preferred content for Fe 3~
5%, Co 0.7~1.2%；The specific surface of catalyst is 10~200m2/ g, preferably 30~150m2/ g, Kong Rongwei 0.2~
0.63ml/g, preferably 0.3~0.55ml/g；Wherein catalyst is to be loaded with active component on carrier by impregnation method, is passed through
Roasting, hydrogen atmosphere reduction are made；Reaction condition：30~80 DEG C, 1.5~3.0MPa of reaction pressure of reactor inlet temperature, it is empty
2000~10000h of speed-1, hydrogen added in using distribution mode, and hydrogen/acetylene volume ratio is 2~20.
2. acetylene hydrogenation method according to claim 1, it is characterised in that use in hydrogenation catalyst, active component Fe master
It will be with α-Fe2O3Form exists, wherein α-Fe2O3The Fe of form will account for more than 50% Fe gross masses.
3. acetylene hydrogenation method according to claim 1, it is characterised in that：Catalyst carrier is aluminium oxide or alumina series
Carrier, alumina series carrier refer to the complex carrier of aluminium oxide and other oxides, and wherein aluminium oxide accounts for the 50% of carrier quality
More than, can be aluminium oxide with silica, zirconium oxide, magnesia compound, preferably alumina-zirconia composite carrier,
Wherein alumina content is more than 60%；Aluminium oxide can be the mixture of θ, α, γ type or its a variety of crystal form, preferably α-
Al2O3Or-the Al containing α2O3Mixing crystal form aluminium oxide.
4. acetylene hydrogenation method according to claim 1, which is characterized in that Fe-Co selective hydrogenation catalysts is used to lead to
Preparation Fe predecessors aqueous solution, Co predecessor aqueous solutions are crossed, difference impregnated carrier is aged, is dry, roasted or mixed with it respectively
Solution impregnating carrier obtains after rear ageing, dry, roasting.
5. acetylene hydrogenation method according to claim 4, it is characterised in that：30~60 DEG C of dipping temperature, dip time 10
~60min, maceration extract pH value 1.5~5.0；20~60 DEG C of Aging Temperature, 30~120min of digestion time；300 DEG C of calcination temperature
~600 DEG C, 240~300min of roasting time, preferably 400~500 DEG C of calcination temperature.
6. acetylene hydrogenation method according to claim 4, it is characterised in that：It is dry to be dried for temperature programming, drying temperature
Program setting is：
7. acetylene hydrogenation method according to claim 4, it is characterised in that：It is roasted to temperature-programmed calcination, calcination temperature
Program setting is：
8. acetylene hydrogenation method according to claim 4, it is characterised in that：Catalyst reduction refers to use N2+H2Gaseous mixture pair
Catalyst is restored, H2Volume content is preferably 10~50%, 200~350 DEG C of reduction temperature, and the recovery time 240~
360min, 60~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；Optimum condition is is gone back at 250~335 DEG C
Original, 200~400h of volume space velocity-1, reduction pressure is preferably 0.1~0.5MPa.
9. acetylene hydrogenation method according to claim 1, it is characterised in that：Methanol-to-olefins device product passes through separation,
Two material of carbon from deethanizer overhead is mainly：Ethylene >=99.9 volume %, 1~10ppm of acetylene 5~100ppm, CO.
10. acetylene hydrogenation method according to claim 1, it is characterised in that adiabatic reactor reactor is single hop reactor.
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| CN102755891A (en) * | 2011-04-28 | 2012-10-31 | 沙索技术有限公司 | Catalysts |
| CN105732266A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Selective hydrogenation method for trace acetylene in methanol-to-olefin device |
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| CN105732261A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Selective hydrogenation method for trace acetylene in methanol-to-olefin device |
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