CN104324731A - Catalyst for producing glycol by virtue of hydrogenation of biodiesel byproduct glycerol and preparation method of catalyst - Google Patents
Catalyst for producing glycol by virtue of hydrogenation of biodiesel byproduct glycerol and preparation method of catalyst Download PDFInfo
- Publication number
- CN104324731A CN104324731A CN201410561796.8A CN201410561796A CN104324731A CN 104324731 A CN104324731 A CN 104324731A CN 201410561796 A CN201410561796 A CN 201410561796A CN 104324731 A CN104324731 A CN 104324731A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- solution
- hydrogenation
- metal
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 128
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 26
- 239000006227 byproduct Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003225 biodiesel Substances 0.000 title claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 238000001994 activation Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims 5
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 239000011261 inert gas Substances 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 abstract description 54
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 11
- 150000002739 metals Chemical class 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000002283 diesel fuel Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000013049 sediment Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000008246 gaseous mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 238000007327 hydrogenolysis reaction Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 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 2
- 239000000463 material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000010792 warming Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明的用于甘油加氢制乙二醇的催化剂，包括以质量百分比计的以下组分：1.0％-10％的活性金属和90-99％的金属氧化物，所述活性金属为具有加氢活性的金属单质，且所述金属氧化物是Fe、Co、Ni、Cu、Zn、Al、Mg、Ce、Zr、Ga氧化物中的一种或两种以上的组合。本发明的生物柴油副产物甘油加氢制乙二醇催化剂价格低、制备简单、活性稳定，有更高的活性和选择性能，甘油转化率100％时产物乙二醇选择性可达60％。
The catalyst for the hydrogenation of glycerol to ethylene glycol of the present invention comprises the following components in terms of mass percent: 1.0%-10% of active metals and 90-99% of metal oxides, the active metals are Hydrogen-active metal element, and the metal oxide is one or a combination of two or more of Fe, Co, Ni, Cu, Zn, Al, Mg, Ce, Zr, and Ga oxides. The biodiesel by-product glycerin hydrogenation ethylene glycol catalyst has low price, simple preparation, stable activity, higher activity and selectivity, and the product ethylene glycol selectivity can reach 60% when the conversion rate of glycerin is 100%.
Description
Technical field
The invention belongs to Green Chemistry living beings and effectively utilize field, be specifically related to a kind of for glycerine (especially as the glycerine of biological diesel oil byproduct) Hydrogenation ethylene glycol catalyst and preparation method thereof.
Background technology
The day by day exhausted energy crisis that result in global range of petroleum resources, the health of the mankind in the environmental pollution that combustion of fossil fuels causes also serious threat, and this two problems has become the bottleneck of restriction society and sustainable economic development.Tapping a new source of energy, walk sustainable development path will be mankind's the only way out.People increase the research dynamics to new forms of energy in recent years, and wind energy, water energy, nuclear energy, solar energy, living beings equal energy source form obtain and greatly develop, and achieve the achievement attracted people's attention.Wherein biomass energy is due to its wide material sources, does not produce unnecessary CO after burning
2, green non-pollution and receive researchers and more and more pay close attention to.
Biodiesel is a kind of substitute products of generally acknowledged reproducible fossil fuel.The rise of Biodiesel all has great significance for alleviating energy crisis, decreasing pollution discharge.Under the effect of catalyst, animal oil, vegetable oil and methyl alcohol or ethanol generation ester exchange reaction are generated fatty acid methyl ester/ethyl ester, generate a large amount of accessory substances simultaneously---glycerine.Usually, the biodiesel often obtaining 10kg just has the glycerine generation of 1kg, and add the industrial use narrow scope of current glycerine, a large amount of remaining glycerine causes glycerine prices, has had a strong impact on the economic benefit of whole Biodiesel chain.How fully utilizing these residue glycerine, make it be converted into have chemicals or the fuel of high added value, is the task that pendulum one of meeting personally scientific worker is urgently to be resolved hurrily at present.
Glycerine is a kind of important chemical products, is widely used as automotive antifreeze, food additives and production cosmetic, explosive, coating or as organic synthesis intermediate.Obtain from triglyceride saponification at first, arrived 1840s, glycerine starts to produce with epoxychloropropane Hydrolyze method on a large scale.Due to the extensive development of Biodiesel in recent years, create excessive crude glycerine product.It is reported, many chemical enterprise giants have turned off the glycerol production factory of many epoxychloropropane routes in succession.This present situation result in the new way that researcher starts to pay close attention to biological diesel oil byproduct glycerin comprehensive utilization.At present, glycerine utilizes to be produced fuels and chemicals and has number of ways, comprises glycerine reformation hydrogen production, hydrogenolysis of glycerin produce diatomic alcohol, glycerine selective oxidation, dehydrating glycerin prepare the methods such as methacrylaldehyde.
The people such as Behr discuss the route preparing various chemicals by glycerine, propose the potential using value that glycerine utilizes.What point out that current glycerine route has application prospect most is that fermentation method prepares 1,3-PD and preparing epoxy chloropropane by using glycerol method.Meanwhile, biological diesel oil byproduct glycerin is utilized to prepare the approach of fuels and chemicals a lot.Main there is glycerine hydrogen manufacturing, hydrogenolysis of glycerin prepares 1,2-PD, 1,3-glycerine, ethylene glycol, etc.Current work mainly concentrates on glycerine route and prepares propane diols, is devoted to hydrogenolysis of glycerin specially and prepares the rarely found of ethylene glycol.Present ethylene glycol is mainly obtained by the hydrolysis of oxirane, its source is the product ethene of petrochemical industry, the ethylene glycol technique of exploitation living beings approach can reduce the dependence to petroleum resources, simultaneously also can decreasing pollution, has very high economic worth and environmental value.
Because dihydroxylic alcohols can be widely used in synthetic resin industry, output is in ascendant trend year by year.Such as 1,2-PD, 1,3-PD, ethylene glycol etc., these dihydroxylic alcohols adopt the preparation of fossil fuel source method at present usually, and these methods consume non-renewable fossil energy, energy consumption is large, seriously polluted, therefore sight turns in the exploitation of renewable alternative energy source by more and more researcher.Use biological diesel oil byproduct glycerin to select hydrogenolysis to prepare the technology of dihydroxylic alcohols, receive due to advantages such as cost of material is low, recyclabilities and pay close attention to more and more widely.
Patent CN101380576A reports a kind of Catalysts and its preparation method of hydrogenolysis of rare glycerol to produce diatomic alcohol, and it is a kind of containing Ni, Co, B tri-kinds of element catalysts that this patent system is standby, adopts NaBH
4or KBH
4reducing process activates, and the conversion ratio of final hydroformylation product solution reaches 83.7%, and glycol selectivity is up to 19.1%.This method for preparing catalyst is complicated, and catalyst activity poor stability, ethylene glycol yield is not high.Disclosed in patent ZL 95121742.9, Co-Cu-Mn-Mo catalyst is at 250 DEG C, H
2pressure is react 6h under 25MPa condition mass fraction can be made to be that 99.5% glycerol conversion yield reaches 100%, the selective of 1,2-PDO reaches 87%, and glycol selectivity is lower, CN 101085719A discloses Cu-Co-Al catalyst at 240 DEG C, the glycerite of 80% concentration can be made under 10MPa in autoclave to transform completely, primary product 1,2-PDO and EG, overall selectivity can reach 95.5%, the pressure that above two patents use is higher, and severe reaction conditions, will increase investment cost.
Summary of the invention
Be propane diols in view of main purpose product in prior art and study less to glycerine hydrogenation preparing ethylene glycol, glycol selectivity is low, the present situation of severe reaction conditions, the object of this invention is to provide a kind of biological diesel oil byproduct glycerin Hydrogenation ethylene glycol catalyst and preparation method thereof.
Catalyst for glycerine hydrogenation preparing ethylene glycol of the present invention, comprise following component by percentage to the quality: the active metal of 1.0%-10% and the metal oxide of 90-99%, described active metal is the metal simple-substance with hydrogenation activity, and described metal oxide is one or more the combination in Fe, Co, Ni, Cu, Zn, Al, Mg, Ce, Zr, Ga oxide.
Active metal described in the catalyst that the present invention is preferential is one or more the combination in Pt, Pd, Ru, Rh, Au.
Described in the catalyst that the present invention is preferential, metal oxide is Fe
2o
3, Co
3o
4, one or more combination in NiO, CuO, ZnO.
Glycerine described in the catalyst that the present invention is preferential is the glycerine water solution as biological diesel oil byproduct.
The present invention also provides a kind of method preparing catalyst of the present invention, comprising:
(1) take each metallic element predecessor by metallic element proportioning each in catalyst, water-soluble formation metallic element predecessor mixed solution, described metallic element predecessor is nitrate, chloride or sulfate;
(2) by water-soluble for precipitating reagent formation precipitant solution;
(3) precipitant solution is added to produce precipitation in the metallic element predecessor mixed solution of stirring, until pH is 8-12;
(4) standing aging;
(5) wash sediment with water to neutral, and drying dewaters; And
(6) described in roasting, dry postprecipitation thing obtains catalyst precursors, then reduction activation process under hydrogen-indifferent gas mixed atmosphere, obtains powder catalyst.
Beneficial effect of the present invention is: catalyst price prepared by the present invention is low, it is simple, activity stabilized to prepare, and have higher activity and selectivity energy, during glycerol conversion yield 100%, glycol product is selective reaches 60%.
Accompanying drawing explanation
Fig. 1 is that the XRD for biological diesel oil byproduct glycerin Hydrogenation ethylene glycol catalyst embodiment 1 of the present invention schemes;
Wherein, (a) 5%Pd/Fe
2o
3after reduction, (b) 5%Pd/Fe
2o
3do not reduce.
The TPR figure of the biological diesel oil byproduct glycerin Hydrogenation ethylene glycol catalyst embodiment 1 of Fig. 2 prepared by the present invention; And
The TEM figure of the biological diesel oil byproduct glycerin Hydrogenation ethylene glycol catalyst embodiment 1 of Fig. 3 prepared by the present invention;
Wherein: (a) 5%Pd/Fe
2o
3(b) 5%Pd/Fe before reduction
2o
3after reduction.
Detailed description of the invention
Of the present invention for biological diesel oil byproduct glycerin Hydrogenation ethylene glycol catalyst, comprise following component by percentage to the quality: 1.0%-10% active metal, 10-99% metal oxide.
Described active metal is the metal simple-substance with hydrogenation activity, can be one or more the combination in Pt, Pd, Ru, Rh, Au.Preferred active component is a kind of in platinum and palladium or both combinations.
Described metal oxide can be one or more the combination in Fe, Co, Ni, Cu, Zn, Al, Mg, Ce, Zr, Ga oxide.Preferred oxide is Fe
2o
3, Co
3o
4, NiO, CuO, ZnO.
Preferably, above-mentioned catalyst comprises the metal oxide of 3%-7% active metal and 93-97%.
Metallic element predecessor described in during Kaolinite Preparation of Catalyst can be nitrate or sulfate.Preferably nitrate.
The preparation of biological diesel oil byproduct glycerin Hydrogenation ethylene glycol catalyst of the present invention comprises the following steps:
Dissolve: two kinds or three kinds of metal nitrates are dissolved in deionized water and stirring and make it dissolve completely.
Precipitation: instillation precipitating reagent, period keeps certain temperature, keeps constant speed, and precipitation slowly produces, and controls terminal pH=7 ~ 12 with pH meter.
Aging: to spend the night under room temperature stops stirring condition aging.
Washing: deionized water washing is to neutral.
Dry: dry 12h at 110 DEG C.
Activation: hydrogen reduction method.
More specifically, catalyst can be prepared according to the following steps:
(1) take each metallic element predecessor by metallic element proportioning each in catalyst with nitrate salts, be dissolved in deionized water, being configured to concentration is in molar ratio the mixed solution that 0.1mol/L is extremely saturated, stirs and fully dissolves;
(2) precipitating reagent is dissolved in deionized water, is configured to the solution that concentration is 0.1 ~ 4.0mol/L in molar ratio;
(3) under tepidarium (such as 60 DEG C), instill precipitating reagent under vigorous stirring in slaine mixed solution with speed (as 10mL/min) slowly, controlling titration end-point pH with pH meter is 8-10, keeps 1h under strong agitation;
(4) maintain tepidarium 60 DEG C constant, stop stirring, leave standstill aging 1 ~ 10h;
(5) step (4) gained mixture is obtained solid sediment through suction filtration, repeatedly add water washing to neutral, drier removing moisture;
(6) through 300 ~ 500 DEG C of roastings, obtain catalyst precursors, under low hydrogen mixed atmosphere, 250 ~ 400 DEG C of prereduction activation process, obtain powder catalyst.
In step (1), preferred concentration is the mixed solution that total mol concentration is about 0.1mol/L.
In step (2), the preferred Na of precipitating reagent
2cO
3or KOH, preferred concentration is the solution of 0.5 ~ 2.0mol/L.
In step (3), precipitation terminal is preferably 8.5 ~ 9.5.
In step (4), ageing time is preferably 6-10h.
In step (5), baking temperature is preferably 80 ~ 120 DEG C, and drying time is preferably 2 ~ 12h.
In step (6), described low hydrogen blender is preferably containing 5-20% especially 10%H
2h
2-N
2gaseous mixture or containing 5-20% especially 10%H
2h
2-Ar gaseous mixture, is preferably 5 ~ 12h with the time of reduction activation process.
With Pd/Fe
2o
3catalyst is example, and its preparation and the application in glycerine hydrogenation preparing ethylene glycol comprise:
Prepared by catalyst precursors
Pd/Fe
2o
3catalyst is prepared by coprecipitation: according to the composition requirement of catalyst, the raw material Fe (NO of accurate weighing respective amount
3)
39H
2o, Pd (NO
3)
32H
2o, adds suitable quantity of water and dissolves, stir.Then the Na of 1.0mol/L is instilled under strong mechanical agitation
2cO
3the aqueous solution, constant temperature 60 DEG C, controls titration end-point with pH meter, and terminal pH is remained on 9.0 ± 0.1.Form coprecipitation mixture.After precipitation is complete, room temperature stops stirring age overnight.By gained precipitation through washing, suction filtration, until neutral.Sample is dry 12h at 110 DEG C, and 300 DEG C of roasting 4h, make catalyst precursors.
The activation process of catalyst
Tubular type Muffle furnace is adopted to carry out activation process.Body of heater is the quartz ampoule of long 100cm, internal diameter 8cm.Put into load weighted catalyst precursor in quartz boat, be placed into flat-temperature zone in the middle of quartz ampoule, closed quartz tube two ends, pass into atmosphere of hydrogen 10min emptying.Be warming up to 200 DEG C from room temperature with the speed program of 2 DEG C/min, after constant temperature 4h, room temperature is down in cooling naturally, obtains catalyst fines.Again with 1%O before catalyst uses
2/ N
2passivation Treatment 12h is carried out to catalyst.
Glycerine aqueous phase hydrogenolysis (catalyst activity test)
The catalyst that 20% glycerine water solution and the 1.0g of 100mL activate is poured simultaneously into the stainless steel autoclave of 250mL, envelope still, is forced into 2.0MPa after washing still 5 times, opens heating by the High Purity Hydrogen of 2.0MPa, rise to after specifying reaction temperature and open stirring 500rpm, reaction starts.After question response proceeds to the fixed time, logical condensed water is down to room temperature.Gas-phase product airbag is collected gas chromatographic analysis, tears still open, take out reactant liquor and carry out gas chromatographic analysis.
Above methods for making and using same is except Pd/Fe
2o
3outward, the preparation of the catalyst of other component according to the invention and the application in glycerine hydrogenation reaction is applicable to too.
Below in conjunction with specific embodiment, the present invention will be further described.
Comparative example 1
Accurately take 0.01mol nickel acetate and 0.01mol cobalt acetate to be dissolved in 40ml water and to mix, join in 150ml flask, in ice-water bath, the NaBH of slow instillation 4.0mol/L under mechanical agitation
4solution, until do not have bubble to produce, stops dripping, after continuing to stir 20min, uses deionized water filtering and washing, finally with absolute ethyl alcohol dehydration, obtain black presoma; Black presoma is placed in vacuum drying chamber vacuum drying 5h under 100 DEG C of conditions, dried presoma with 5% H
2-N
2gaseous mixture activating pretreatment 12h at 250 DEG C obtains black catalyst powder, and catalyst consists of 36%-37%Co-27%B.
The test of catalyst activity is carried out in 250ml autoclave, at 200 DEG C, hydrogenation reaction 12h under 4.0MPa, the results are shown in Table 1.
Comparative example 2
Cu-Zn-Ti (1:2:1) catalyst is prepared by coprecipitation: according to the composition requirement of catalyst, takes the raw material Cu (NO of respective amount
3) 3H
2o, Zn (NO
3)
36H
2o and TiCl
4mixing, adds suitable quantity of water dissolving and stirs.Then under 75 DEG C of constant temperature, above-mentioned mixed liquor and saturated sodium carbonate are instilled in beaker side by side.Abundant stirring, makes the pH of reactant liquor remain between 8 ~ 8.5, forms coprecipitation mixture.After precipitation is complete, aged overnight.By gained precipitation after washing, decant, suction filtration, dry 12h at 120 DEG C, 450 DEG C of roasting 2h, form catalyst Precursors.Reaction is carried out in fixed bed reactors, and before reaction, catalyst Precursors uses 10%H at needing 280 DEG C
2-N
2gaseous mixture reductase 12 h.The results are shown in Table 1.
Embodiment 1
Accurate weighing 0.1266g palladium nitrate and 5.071g ferric nitrate are dissolved in 200ml deionized water, mix and join in 500ml flask, in 60 DEG C of tepidarium, slowly instill the Na of 1.0mol/L under mechanical agitation
2cO
3solution, controls terminal pH=9.0 with pH meter, stops dripping, and after continuing to stir 30min, maintains water bath with thermostatic control temperature-resistant, stops stirring, aging 5h.Use deionized water filtering and washing, obtain solid sediment; Sediment is placed in air dry oven dry 12h at 110 DEG C, after grinding, obtains pulverulent solids, be placed in Muffle furnace 300 DEG C of roasting 5h, obtain black powder catalyst precursor; Presoma 10%H after roasting
2-N
2gaseous mixture activating pretreatment 4h at 200 DEG C obtains black catalyst powder, and catalyst consists of 5%Pd-95%Fe
2o
3.For preventing Oxidative inactivation in air, need at 1.0%O before using
2/ N
2passivation 12h in atmosphere.
The test of catalyst activity is carried out in 250ml autoclave, first in autoclave, add the 20%wt glycerine water solution of 100ml, drop in the catalyst of pure glycerin quality 5%, the required pressure of reaction is charged to for several times with high-purity hydrogen gas washing, in 220 DEG C, hydrogenation reaction 12h under 4.0MPa, after having reacted, liquids and gases product adopts gas-chromatography FID and TCD detector to detect respectively and analyzes, and the catalyst formulation of glycerine water solution hydrogenolysis preparing ethylene glycol and reaction result are in table 1.
Embodiment 2
Accurate weighing 0.1266g palladium nitrate and 4.9383g cobalt nitrate are dissolved in 200ml deionized water, mix and join in 500ml flask, in 60 DEG C of tepidarium, slowly instill the Na of 1.0mol/L under mechanical agitation
2cO
3solution, controls terminal pH=9.0 with pH meter, stops dripping, and after continuing to stir 30min, maintains water bath with thermostatic control temperature-resistant, stops stirring, aging 5h.Use deionized water filtering and washing, obtain solid sediment; Sediment is placed in air dry oven dry 12h at 110 DEG C, after grinding, obtains pulverulent solids, be placed in Muffle furnace 300 DEG C of roasting 5h, obtain black powder catalyst precursor; Presoma 10%H after roasting
2-N
2gaseous mixture activating pretreatment 4h at 200 DEG C obtains black catalyst powder, and catalyst consists of 5%Pd-95%Co
3o
4.For preventing Oxidative inactivation in air, need at 1.0%O before using
2/ N
2passivation 12h in atmosphere.
The test of catalyst activity is carried out in 250ml autoclave, at 200 DEG C, hydrogenation reaction 12h under 4.0MPa, the results are shown in Table 1.
Embodiment 3
Accurate weighing 0.1266g palladium nitrate and 4.9554g nickel nitrate are dissolved in 200ml deionized water, mix and join in 500ml flask, in 60 DEG C of tepidarium, slowly instill the Na of 1.0mol/L under mechanical agitation
2cO
3solution, controls terminal pH=9.0 with pH meter, stops dripping, and after continuing to stir 30min, maintains water bath with thermostatic control temperature-resistant, stops stirring, aging 5h.Use deionized water filtering and washing, obtain solid sediment; Sediment is placed in air dry oven dry 12h at 110 DEG C, after grinding, obtains pulverulent solids, be placed in Muffle furnace 300 DEG C of roasting 5h, obtain black powder catalyst precursor; Presoma 10%H after roasting
2-N
2gaseous mixture activating pretreatment 4h at 200 DEG C obtains black catalyst powder, and catalyst consists of 5%Pd-95%NiO.For preventing Oxidative inactivation in air, need at 1.0%O before using
2/ N
2passivation 12h in atmosphere.
The test of catalyst activity is carried out in 250ml autoclave, at 200 DEG C, hydrogenation reaction 12h under 4.0MPa, the results are shown in Table 1.
Table 1
Embodiment 4 ~ 10
Accurate weighing 0.1266g palladium nitrate and 5.071g nickel nitrate are dissolved in 200ml deionized water, mix and join in 500ml flask, in 60 DEG C of tepidarium, slowly instill the Na of 1.0mol/L under mechanical agitation
2cO
3solution, controls terminal pH=9.0 with pH meter, stops dripping, and after continuing to stir 30min, maintains water bath with thermostatic control temperature-resistant, stops stirring, aging 5h.Use deionized water filtering and washing, obtain solid sediment; Sediment is placed in air dry oven dry 12h at 110 DEG C, after grinding, obtains pulverulent solids, be placed in Muffle furnace 300 DEG C of roasting 5h, obtain black powder catalyst precursor; Presoma 10%H after roasting
2-N
2gaseous mixture activating pretreatment 4h at 200 DEG C obtains black catalyst powder, and catalyst consists of 5%Pd-95%NiO.For preventing Oxidative inactivation in air, need at 1.0%O before using
2/ N
2passivation 12h in atmosphere.
The test of catalyst activity is carried out in 250ml autoclave, the results are shown in Table 2.
Table 2
| Embodiment | Reaction temperature/DEG C | Reaction pressure/MPa | Glycerol conversion yield/% | Glycol selectivity/% |
| 4 | 180 | 4.0 | 75.75 | 42.5 |
| 5 | 200 | 4.0 | 86.88 | 55.6 |
| 6 | 220 | 4.0 | 99.84 | 60.1 |
| 7 | 240 | 4.0 | 100 | 57.5 |
| 8 | 220 | 2.0 | 95.60 | 56.4 |
| 9 | 220 | 6.0 | 100 | 57.3 |
| 10 | 220 | 8.0 | 100 | 55.6 |
Embodiment 11-14
Accurate weighing 0.1266g palladium nitrate and 5.071g nickel nitrate are dissolved in 200ml deionized water, mix and join in 500ml flask, in 60 DEG C of tepidarium, slowly instill the Na of 1.0mol/L under mechanical agitation
2cO
3solution, controls terminal pH=9.0 with pH meter, stops dripping, and after continuing to stir 30min, maintains water bath with thermostatic control temperature-resistant, stops stirring, aging 5h.Use deionized water filtering and washing, obtain solid sediment; Sediment is placed in air dry oven dry 12h at 110 DEG C, after grinding, obtains pulverulent solids, be placed in Muffle furnace 300 DEG C of roasting 5h, obtain black powder catalyst precursor; Presoma 10%H after roasting
2-N
2gaseous mixture activating pretreatment 4h at 200 DEG C obtains black catalyst powder, and catalyst consists of 5%Pd-95%NiO.For preventing Oxidative inactivation in air, need at 1.0%O before using
2/ N
2passivation 12h in atmosphere.
The test of catalyst activity is carried out in 250ml autoclave, at 220 DEG C, hydrogenation reaction 12h under 4.0MPa, the results are shown in Table 3.
Table 3
| Embodiment | Number of repetition | Glycerol conversion yield/% | Glycol selectivity/% |
| 11 | 2 | 97.54 | 59.10 |
| 12 | 3 | 96.12 | 58.64 |
| 13 | 4 | 95.76 | 56.55 |
| 14 | 5 | 93.92 | 57.35 |
Above-described embodiment is only the preferred embodiment for the present invention; such as; biological diesel oil byproduct glycerin Hydrogenation ethylene glycol catalyst of the present invention is not only applicable to catalytic reaction of the present invention; generally can also be applicable to the reaction of all kinds of hydrogenation catalyst; therefore limiting the scope of the invention can not be regarded as, the change of any unsubstantiality that the technology of this area is done on basis of the present invention and replace and all belong to the scope of protection of the invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410561796.8A CN104324731A (en) | 2014-10-21 | 2014-10-21 | Catalyst for producing glycol by virtue of hydrogenation of biodiesel byproduct glycerol and preparation method of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410561796.8A CN104324731A (en) | 2014-10-21 | 2014-10-21 | Catalyst for producing glycol by virtue of hydrogenation of biodiesel byproduct glycerol and preparation method of catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104324731A true CN104324731A (en) | 2015-02-04 |
Family
ID=52399609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410561796.8A Pending CN104324731A (en) | 2014-10-21 | 2014-10-21 | Catalyst for producing glycol by virtue of hydrogenation of biodiesel byproduct glycerol and preparation method of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104324731A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114247451A (en) * | 2021-12-31 | 2022-03-29 | 厦门欧米克生物科技有限公司 | Glycerol hydrogenation catalyst, and preparation method and application thereof |
| CN114733530A (en) * | 2022-03-29 | 2022-07-12 | 西安交通大学 | A kind of hydrogenation catalyst of organic liquid hydrogen storage carrier and preparation method and application thereof |
| CN115487814B (en) * | 2021-06-18 | 2024-03-26 | 中国石油化工股份有限公司 | Dual-function catalyst, preparation method and application thereof, and method for preparing glycol from carbohydrate raw material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020165092A1 (en) * | 2000-12-29 | 2002-11-07 | Qianwen Zhang | Catalyst for selective hydrogenation, its preparation process and application |
| CN101054339A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
| CN101372444A (en) * | 2007-08-24 | 2009-02-25 | 中国科学院大连化学物理研究所 | A kind of method of hydrocracking of glycerol |
-
2014
- 2014-10-21 CN CN201410561796.8A patent/CN104324731A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020165092A1 (en) * | 2000-12-29 | 2002-11-07 | Qianwen Zhang | Catalyst for selective hydrogenation, its preparation process and application |
| CN101054339A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
| CN101372444A (en) * | 2007-08-24 | 2009-02-25 | 中国科学院大连化学物理研究所 | A kind of method of hydrocracking of glycerol |
Non-Patent Citations (3)
| Title |
|---|
| MARIA GRAZIA MUSOLINO ET AL.: "Glycerol Hydrogenolysis Promoted by Supported Palladium Catalysts", 《CHEMSUSCHEM》 * |
| TAO JIANG ET AL.: "Catalytic performance of Pd-Ni bimetallic catalyst for glycerol hydrogenolysis", 《BIOMASS AND BIOENERGY》 * |
| 江涛: "含镍双金属催化剂上有/无外供氢条件下甘油氢解性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115487814B (en) * | 2021-06-18 | 2024-03-26 | 中国石油化工股份有限公司 | Dual-function catalyst, preparation method and application thereof, and method for preparing glycol from carbohydrate raw material |
| CN114247451A (en) * | 2021-12-31 | 2022-03-29 | 厦门欧米克生物科技有限公司 | Glycerol hydrogenation catalyst, and preparation method and application thereof |
| CN114247451B (en) * | 2021-12-31 | 2023-12-22 | 厦门欧米克生物科技有限公司 | Glycerol hydrogenation catalyst and preparation method and application thereof |
| CN114733530A (en) * | 2022-03-29 | 2022-07-12 | 西安交通大学 | A kind of hydrogenation catalyst of organic liquid hydrogen storage carrier and preparation method and application thereof |
| CN114733530B (en) * | 2022-03-29 | 2023-11-03 | 陕西氢易能源科技有限公司 | Hydrogenation catalyst of organic liquid hydrogen storage carrier, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104959158B (en) | Mo2C/CdS composite photocatalyst and preparation and application thereof | |
| CN102716744B (en) | Preparation method for synthesizing copper-based catalyst by sol-gel ammonia still process | |
| CN103170339B (en) | Cu base high-temperature water gas conversion catalyst and preparation method thereof in a kind of hydrogen-rich atmosphere | |
| CN103816908A (en) | Catalyst for preparing alcohol by hydrogenising acetate and preparation method of catalyst | |
| CN104028270A (en) | Methanation catalyst and preparation method thereof | |
| CN106311242B (en) | A kind of carbon dioxide methanation catalyst and preparation method thereof | |
| CN101485983A (en) | Catalyst for hydrogen production from dimethyl ether-steam reforming and preparation method thereof | |
| CN104785261B (en) | Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof | |
| CN104549412A (en) | A kind of mesoporous metal oxide catalyst and preparation method for photocatalytic reduction of CO2 | |
| CN102145287A (en) | Catalyst for synthesizing methanol from hydrogenated carbon dioxide and preparation method of catalyst | |
| CN106669743B (en) | A kind of reforming hydrogen production catalyst and preparation method thereof | |
| CN102794180A (en) | Preparation of copper-cerium hydrogenation catalyst and catalytic cellulose hydrogenation method thereof | |
| CN103599790A (en) | Cobalt rare earth composite oxide catalyst for efficiently catalyzing complete oxidation of methane at low temperature | |
| CN113842914A (en) | A catalyst for synthesizing methanol from carbon dioxide and its preparation method and application | |
| CN104324731A (en) | Catalyst for producing glycol by virtue of hydrogenation of biodiesel byproduct glycerol and preparation method of catalyst | |
| CN113145113A (en) | Carbon dioxide hydrogenation catalyst, preparation method and application thereof | |
| CN101455965B (en) | Low steam-gas ratio transformation catalyst in hydrogen rich gas and preparation method thereof | |
| CN103537288A (en) | Method for preparing methanation catalyst by adopting urea combustion method | |
| CN107774269A (en) | Co deposited synthesis copper ceria catalyst, preparation method and application | |
| CN101829578A (en) | Catalyst for catalyzing and reforming biologic oil to prepare hydrogen and preparation method thereof | |
| CN104028267A (en) | Method for preparing cyclohexane precious metal Ru catalyst by benzene selective hydrogenation | |
| CN101565358A (en) | Method for directly synthesizing dimethyl ether by CO2 of slurry reactor | |
| CN101428222A (en) | Catalyst for producing 1,2-propylene glycol with glycerol hydrogenolysis and preparation method thereof | |
| CN100462299C (en) | Method for producing synthesis gas by steam reforming of glycerin, a by-product of biodiesel production | |
| CN103191732A (en) | Method for preparing cyclohexene catalyst through partial hydrogenation of benzene, and method for producing cyclohexene through using cyclohexene catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150204 |