CN101993349A - Method for producing glycol by using oxalic ester - Google Patents
Method for producing glycol by using oxalic ester Download PDFInfo
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- CN101993349A CN101993349A CN2009100578557A CN200910057855A CN101993349A CN 101993349 A CN101993349 A CN 101993349A CN 2009100578557 A CN2009100578557 A CN 2009100578557A CN 200910057855 A CN200910057855 A CN 200910057855A CN 101993349 A CN101993349 A CN 101993349A
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 150000002148 esters Chemical class 0.000 title claims abstract description 38
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052802 copper Inorganic materials 0.000 claims abstract description 61
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 68
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 40
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical group CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 34
- 239000002609 medium Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000011877 solvent mixture Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002826 coolant Substances 0.000 abstract description 15
- 238000009776 industrial production Methods 0.000 abstract 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 48
- 238000005984 hydrogenation reaction Methods 0.000 description 40
- 239000007789 gas Substances 0.000 description 15
- 230000009466 transformation Effects 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 230000008676 import Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- -1 frostproofer Polymers 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 229910017813 Cu—Cr Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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Abstract
The invention relates to a method for producing glycol by using oxalic ester, mainly solving the problems of the prior art that the radial temperature difference in a reactor is large and the selectivity of the target product glycol is lower. In the method, oxalic ester and hydrogen are used as raw materials, the mole ratio of the hydrogen to the oxalic ester is 40-200:1, fatty alcohol with 1-4 carbons is used as a solvent, the weight percent of the solvent to the oxalic ester in the raw materials is 0-0.9:1; the conditions of the method are follows: at least one of the oxalic ester, the hydrogen and the solvent is used as a cooling medium, the temperature is 160 DEG C-280 DEG C, the pressure is 1.0-6.0MPa, weight airspeed is 0.1-10h<-1> with reference to the weight of the mixture of the oxalic ester and the solvent, and the mole ratio of the hydrogen to the oxalic ester is 40-200:1; the cooling medium passes through a tube in a tube type fixed bed reactor; a catalyst bed layer is arranged outside the tube; and after being uniformly mixed together, the cooling medium and the mixture of the fresh raw materials and the solvent enter the reactor and contact a copper containing catalyst outside the tube to react to generate glycol, wherein the flowing direction of the cooling medium is identical to or opposite to the flowing direction of the mixture of the raw materials and the solvent, and the weight percentage of the oxalic ester is not less than 10%. The method disclosed in the invention better solves the problems of the prior art and can be used in the industrial production of glycol.
Description
Technical field
The present invention relates to a kind of method, in particular, relate to a kind of method of producing ethylene glycol at the calandria type fixed bed reactor mesoxalic acid dimethyl ester or the oxalic acid diethyl ester hydrogenation of inner tubulation heat exchange with preparing ethylene glycol from oxalic ester.
Background technology
Ethylene glycol (EG) is a kind of important petrochemical complex basic organic material, and it can be mixed with arbitrary proportion and water, and boiling point height, zero pour are low.Be mainly used in and produce trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used for industries such as coating, soup, brake fluid and printing ink in addition, solvent and medium as ammonium pertorate, be used to produce special solvent glycol ether etc., purposes is very extensive.
At present, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts the operational path of oxyethane direct hydration method, promptly earlier through the petroleum path synthesizing ethylene, reoxidizes ethylene production oxyethane, obtains EG by oxyethane on-catalytic hydration reaction at last.Production technology is monopolized by Dutch Shell, U.S. Halcon-SD and U.S. UCC three companies basically.The economic benefit of this production technique is owing to be subjected to the restriction of oil price, and it is bigger to fluctuate.In order to overcome above-mentioned shortcoming and to reduce production costs, since the seventies in 20th century, having begun green route gradually is the C of raw material with matchmaker, Sweet natural gas or heavy wet goods low-cost resource promptly
1Chemical research becomes the eighties of heat subject in the world.Wherein from synthetic gas, at first by CO gas-phase catalytic coupling synthesis of oxalate, barkite shortening is again produced ethylene glycol, with its raw material sources extensively and numerous advantages such as cheap, Technological Economy height, and enjoys attention.
Adopt the technology of producing ethylene glycol from hydrogenation of oxalic ester can be divided into based on the liquid phase homogeneous hydrogenation method of noble metal catalysts such as Ru with based on the heterogeneous gas phase or the liquid-phase hydrogenatin method of copper-based catalysts.Wherein, homogeneous phase liquid-phase hydrogenatin need under high pressure be carried out, and speed of reaction is slow, and product separation reclaims difficulty, there are shortcomings such as selectivity is low in the heterogeneous liquid phase catalytic hydrogenation of loading type, has better conversion rate and selectivity and adopt loaded catalyst to carry out gas phase hydrogenation.External many companies have done research to this technology, and be oneself the barkite hydrogenation catalyst and the technology application patent.Surplus emerging product of Japan beginning of the eighties, a large amount of research has been carried out in the application in hydrogenation of oxalate for preparing ethylene glycol reacts to copper base chromium-free catalyst.Wherein clear 57-122946, clear 57-123127, clear 57-180432, clear 57-122938, clear 57-122941 has delivered about the catalyzer based on copper, has investigated carrier (Al
2O
3, SiO
2, La
2O
3Deng), auxiliary agent (K, Zn, Ag, Mo, Ba etc.), preparation method etc. are to catalyst activity and optionally influence.The mid-80, ARCO company disclosed the Cu-Cr catalyzer that is used for barkite gas phase hydrogenation preparing ethylene glycol at U.S. Pat P4677234 in 1986, and sulfur impurity, iron level in catalyzer and the raw material defined made strict regulation, requirement is below 4ppm, obtained the ethylene glycol of 95% yield under about 30atm pressure, the long running time of this catalyzer is 466h.In the same year, surplus emerging product and UCC unite in the 309th～321 page of 1987 the 31st volume of document " Applied Catalysis " and have reported the Cu/SiO that adopts cupric ammine complex and preparation of silica gel
2Catalyzer is under 215 ℃, 0.3MPa pressure, and the yield of ethylene glycol is up to 97.2%.1994 Nian Ange companies have reported oxide compound and a small amount of Al of Cu-Zn in patent USP5345005
2O
3Catalyzer, also obtained good effect.
Domestic to barkite hydrogenation research more mainly contain University Of Tianjin's carbon one chemical engineering experiment chamber, East China University of Science and Fujian Inst. of Matter Structure, Chinese Academy of Sciences, Fujian thing structure since the research of just relevant CO catalytically synthesizing glycol of nineteen eighty-two, be that domestic progress is fast, scale greatly, one of the unit of the most fruitful research.They have reported that raw materials such as employing cupric nitrate, chromic trioxide, silicon ester, ammoniacal liquor are equipped with loading type Cu-Cr catalyzer with coprecipitation method and gel-sol legal system in the 24th～27 page of document " Industrial Catalysis " 1996 4 phase of ground, be that 2.5～3.0Mpa, temperature are that 208～230 ℃, LHSV are 0.1～0.5h at pressure
-1, the gas ester is than being under 40～60 the condition, running 1134h, the oxalic acid diethyl ester average conversion is 99.8%, the average selectivity of ethylene glycol is 95.3%.University Of Tianjin adopts Cu/SiO
2Catalyzer, to 200～250 ℃, below the 3.0MPa, hydrogen ester is than 30～100, liquid hourly space velocity 0.1875～1.815h
-1Study in the scope, its optimum is an oxalic acid diethyl ester transformation efficiency 95%, ethylene glycol yield about 80%.East China University of Science adopts Cu/SiO
2Catalyzer is also studied preparation of ethanediol by dimethyl oxalate hydrogenation, and top condition is that 210～220 ℃ of temperature of reaction, reaction pressure are that 2.5MPa, hydrogen ester ratio are 60, liquid hourly space velocity 0.65h
-1
The technology of being reported in above-mentioned patent or the document mainly concentrates on the catalyzer and the technical study of preparing glycol by hydrogenating oxalate, has the problem of the poor stability of catalyzer, and the reactor types that is adopted is not appeared in the newspapers.And reactor is as one of nucleus equipment of producing ethylene glycol from hydrogenation of oxalic ester industrial installation, and its performance quality directly influences the utilization ratio of reaction effect, catalyzer and the quality of product.
As everyone knows, hydrogenation reaction is thermopositive reaction, and the reaction of producing ethylene glycol from hydrogenation of oxalic ester is no exception equally.For exothermic catalytic reaction, along with the carrying out of reaction process, the reaction heat of constantly emitting can make reaction bed temperature improve, and the inactivation of the inevitable accelerator activator of too high local temperature rise, influences the utilising efficiency of reaction effect and reactor.In order to improve the efficient of reactor, need shift out reaction heat to reduce temperature of reaction.In industrial reactor, once widely use a kind of be that the cold shock of multistage unstripped gas reduces temperature of reaction, this reactor has also reduced reactant concn during because of the unstripped gas cold shock when reducing temperature of reactor, influenced reaction efficiency.Therefore various improved forms have appearred, disclose a kind of heterogeneous synthetic improving one's methods and reactor as Chinese patent CN1030878, but this reactor is not promptly eliminated the cold shock raw material fully and indirect heat exchanger is established in the influence of reactant concn is again made the device structure complexity in bed.Another kind is as disclosed shell and tube reactor among the patent DE2123950, unstripped gas enters from the top inlet mouth and is distributed in each tubulation, with the catalyzer contact reacts in the tubulation, lateral inflow between tubulation, reaction heat is moved heat continuously by the outer boiled water of tubulation, produce steam and gone out by the side pipe, reaction gas goes out reactor by the bottom escape pipe.Though have a narrow range of temperature in this reactor, the catalyst loading coefficient is little, there is serious wall effect in the reactor catalyst bed, influences the space-time yield of catalyzer, and the difficulty that maximizes.
Summary of the invention
Technical problem to be solved by this invention is that the reactor inside diameter that exists in the conventional art is big to the temperature difference, easily cause catalyzer temperature runaway, inactivation and the low problem of purpose glycol product selectivity, a kind of new method with preparing ethylene glycol from oxalic ester is provided, this method has reactor inside diameter to having a narrow range of temperature, barkite transformation efficiency height, glycol selectivity is good, characteristics such as energy efficient.
For solving the problems of the technologies described above, the present invention adopts technical scheme as follows: a kind of method with preparing ethylene glycol from oxalic ester, with barkite and hydrogen is raw material, the mol ratio of hydrogen and barkite is 40～200: 1, Fatty Alcohol(C12-C14 and C12-C18) with 1～4 carbon is a solvent, the weight percent of solvent and raw material medium-height grass acid esters is 0～0.9: 1, with at least a in barkite, hydrogen or the solvent is heat-eliminating medium, in temperature is 160 ℃～280 ℃, pressure is 1.0～6.0MPa, is that the weight space velocity of benchmark is 0.1～10h with the mixture weight of barkite and solvent
-1Hydrogen/ester mol ratio is under 40～200: 1 the condition, pass through in the tubulation of heat-eliminating medium in the calandria type fixed bed reactor, beds is positioned at outside the tubulation, enter in the reactor behind heat-eliminating medium and fresh feed and the solvent mixture uniform mixing, the copper containing catalyst contact reacts outer with tubulation generates ethylene glycol, and wherein the flow direction of the flow direction of heat-eliminating medium and raw material and solvent mixture shows the same direction or opposite directions, the weight percentage of barkite 〉=10%.
In the technique scheme, the operational condition of reactor is: temperature of reaction is 180～260 ℃, is that the weight space velocity of benchmark is 0.1～6h with the mixture weight of barkite and solvent
-1, hydrogen/ester mol ratio is 60～180: 1, and reaction pressure is 1.5～6.0MPa, and the weight percentage of barkite is 10～100%.When barkite was dimethyl oxalate, solvent was a methyl alcohol.When barkite was oxalic acid diethyl ester, solvent was an ethanol.Copper containing catalyst is with silicon oxide, aluminum oxide, at least a in the molecular sieve is carrier, active ingredient is selected from metallic copper, the oxide compound of copper or its mixture, auxiliary agent is selected from zinc, barium, magnesium, at least a in the oxide compound of manganese or chromium metal or its metal, with the carrier is benchmark, weight in elemental copper, be selected from metallic copper, the oxide compound of copper or the consumption of its mixture are that weight content is 5%～50%, preferable range is 10%～40%, weight in the auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal or promoter metal is that weight content is 0.05～15%, and preferable range is 0.1%～10%.Copper containing catalyst is carrier with the silicon oxide, active ingredient is selected from the oxide compound of copper, auxiliary agent is selected from least a in the oxide compound of the oxide compound of oxide compound, barium of zinc or chromium, with the carrier is benchmark, and in the weight of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 10%～35%, preferable range is 15%～30%, in the weight of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal is that weight content is 0.1～5%, and preferable range is 0.5%～5%.
As everyone knows, hydrogenation reaction is thermopositive reaction, and the reaction of producing ethylene glycol from hydrogenation of oxalic ester is no exception equally.Studies show that in a large number, the major cause of barkite hydrogenation catalyst inactivation is catalyst junction carbon and active ingredient grain growth sintering, and the concentrated heat release of hydrogenation process can cause the higher temperature rise of catalyzer, especially the temperature of catalyst active center may exceed catalyzer apparent tens the degree in addition more than 100 ℃, and too high local temperature rise is very fatal to the influence of catalyst life, not only can aggravate catalyzer green coke process greatly, and can quicken growing up of crystal grain greatly, thereby the inactivation of accelerator activator, shorten stable period.Research also shows, for oxalate hydrogenation, is typical cascade reaction, at first the barkite hydrogenation generates the intermediate product ethyl glycolate, the ethyl glycolate repeated hydrogenation generates ethylene glycol, and the ethylene glycol excessive hydrogenation then generates by product ethanol, and high temperature helps the carrying out of side reaction.In addition, being usually used in the multistage cold shock formula fixed-bed reactor of exothermic catalytic reaction and shell and tube reactor is used for this oxalate hydrogenation and all has certain shortcoming, the former is owing to also reduced reactant concn during the unstripped gas cold shock when reducing temperature of reactor, influenced reaction efficiency, thereby must influence the selectivity of the transformation efficiency and the ethylene glycol of barkite, (the tubulation diameter is generally 25～50mm) and the latter is owing to tubulation is thin, catalyzer is contained in the tubulation, exist the packing factor of catalyzer little, there is serious wall effect in the reactor catalyst bed, influence the shortcoming of the space-time yield of catalyzer, thereby when being used for oxalate hydrogenation, must influence the selectivity of the transformation efficiency and the ethylene glycol of barkite, and this reactor maximizes difficult.The new method that the present invention proposes with preparing ethylene glycol from oxalic ester; taken into full account the heat effect of oxalate hydrogenation; on the one hand; by heat exchanging pipe is set in reactor; logical heat-eliminating medium in the heat exchanging pipe; heat exchanging pipe is adorned the scheme of catalyzer outward; not only increased the packing factor of catalyst in reactor; and realized in time removing when reaction liberated heat; reduced the operation temperature rise of reactor; avoided the heat release of hydrogenation concentrations to cause the too high problem that easily causes catalyzer temperature runaway and inactivation of local temperature rise in the beds; guaranteed optimal reaction temperature; optimize the operation operating mode of hydrogenation reaction, effectively protected the reactivity worth of catalyzer, can reach the stable period of maximized prolongation catalyzer; and the transformation efficiency of raising barkite and the optionally purpose of purpose glycol product; on the other hand, remove reaction heat as heat-eliminating medium, saved investment and the energy consumption of advancing the reactor interchanger by adopting unstripped gas.
Adopt technical scheme of the present invention, with dimethyl oxalate or oxalic acid diethyl ester and hydrogen is raw material, methyl alcohol or ethanol are solvent, at least a in barkite, hydrogen or the solvent is heat-eliminating medium, in temperature of reaction is 180～260 ℃, is that the weight space velocity of benchmark is 0.1～6h with the mixture weight of barkite and solvent
-1Hydrogen/ester mol ratio is 60～180: 1, reaction pressure is 1.5～6.0MPa, the weight percentage of barkite is 10～100%, copper containing catalyst is carrier with the silicon oxide, active ingredient is selected from the oxide compound of copper, auxiliary agent is selected from the oxide compound of zinc, at least a in the oxide compound of barium or the oxide compound of chromium, with the carrier is benchmark, weight in elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 10%～35%, and in the weight of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal is that weight content is under 0.1～5% the condition, the same radial section temperature difference of catalyst in reactor bed is less than 6 ℃, the transformation efficiency of barkite is greater than 98%, and the selectivity of ethylene glycol has obtained better technical effect greater than 90%.
Description of drawings
Fig. 1 is calandria type fixed bed reactor and reactor external equipment pipeline interface chart.
Among Fig. 1, A is a material inlet, and B is the product outlet, and C is a cooling medium inlet, and D is the heat-eliminating medium outlet, 1 is little cylindrical shell, and 2 is flange, and 3 is dividing plate, and 4 is stuffing box, 5 is upper cover, and 6 is upper conduit, and 7 is last endless tube, and 8 is housing, 9 is heat exchanging pipe, and 10 are following endless tube, and 11 is bracing frame, and 12 is overflow pipe, 13 is house steward, and 14 is lower cover, and 15 is porous gas collection plate, and 16 is catalyzer, 17,18,19 is pipeline, and M is a mixing tank.
Fig. 1 Raw workflow is: contain oxalate, at least a cooling medium in hydrogen or the solvent is introduced by the cooling medium inlet (C) of reactor, be distributed to each downcomer (12) through house steward (13), be distributed in each the arrangement pipe (9) that is connected in lower endless tube through lower endless tube (10) again, flow up or down and absorb the reaction heat of the outer beds (16) of tubulation, passing dividing plate through upper endless tube (7) and the upper conduit that is connected endless tube (6) enters in the little cylindrical shell (1), going out reactor through the cooling medium at top outlet (D) again enters in the blender (M), with the fresh hydrogen after the preheating of the pipeline (17) that comes, and the fresh oxalate after pipeline (18) preheating that comes and solvent mixture are blender (M) in evenly after the mixing, drawn by pipeline (19), enter in the calandria type fixed bed reactor through material inlet (A) then, with catalyst (16) haptoreaction in the outer beds of tubulation, simultaneously with heat exchanging pipe (9) in the refrigerating gas heat exchange, the reaction effluent that contains ethylene glycol that goes out beds is drawn by the product outlet (B) of reactor through porous gas collection plate (15) to the bottom, obtains the ethylene glycol product through separation.
The invention will be further elaborated by embodiment below in conjunction with accompanying drawing, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Press Fig. 1, it is 2 meters that the dimethyl oxalate hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Zn/SiO
2Catalyzer, in the weight of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 35%, in the weight of simple substance zinc, the consumption that is selected from the oxide compound of zinc is that weight content is 5%.Heat-eliminating medium is dimethyl oxalate and carbinol mixture.With temperature is 160 ℃, the dimethyl oxalate weight percentage is that 25% dimethyl oxalate and carbinol mixture are introduced by cooling medium inlet, be diverted in each heat exchanging pipe, being reverse direction with the flow direction of outer raw material of tubulation and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation is warming up to 210 ℃, draw reactor through the heat-eliminating medium outlet then, enter in the mixer, with fresh hydrogen after the exterior tubing preheating that comes and dimethyl oxalate weight percentage be 25% dimethyl oxalate and carbinol mixture uniform mixing in mixing tank, the weight percentage that mixes the back dimethyl oxalate is 25%, hydrogen and dimethyl oxalate mol ratio are 110: 1, temperature is 210 ℃, enter in the reactor through the reactor feedstocks import again, with the outer copper containing catalyst contact reacts of tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 210 ℃, is that the weight space velocity of benchmark is 1.2h with dimethyl oxalate and methanol mixture weight
-1, hydrogen/ester mol ratio is 110: 1, reaction pressure is 3.2MPa.Under above structural parameter and condition, by the present invention the dimethyl oxalate hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 4 ℃, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethylene glycol is 97.7%, but energy efficient is the 11.7KJ/mol dimethyl oxalate.
[embodiment 2]
Press Fig. 1, it is 2.5 meters that the dimethyl oxalate hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Cr/SiO
2Catalyzer, in the weight of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 25%, in the weight of simple substance chromium, the consumption that is selected from the oxide compound of chromium is that weight content is 10%.Heat-eliminating medium is the mixed gas that dimethyl oxalate, methyl alcohol and hydrogen are formed.With temperature is 170 ℃, the dimethyl oxalate weight percentage is that the unstripped gas that 50% dimethyl oxalate and carbinol mixture and hydrogen are formed is introduced by cooling medium inlet, be diverted in each heat exchanging pipe, being reverse direction with the flow direction of outer raw material of tubulation and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation is warming up to 230 ℃, draw reactor through the heat-eliminating medium outlet then, enter in the mixer, with fresh hydrogen after the exterior tubing preheating that comes and dimethyl oxalate weight percentage be 50% dimethyl oxalate and carbinol mixture uniform mixing in mixing tank, the weight percentage that mixes the back dimethyl oxalate is 50%, hydrogen and dimethyl oxalate mol ratio are 120: 1, temperature is 230 ℃, again in material inlet is introduced shell and tube reactor, with the outer copper containing catalyst contact reacts of tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 230 ℃, is that the weight space velocity of benchmark is 0.7hr with dimethyl oxalate and methanol mixture weight
-1, hydrogen/ester mol ratio is 120: 1, reaction pressure is 3.8MPa.Under above structural parameter and condition, by the present invention the dimethyl oxalate hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 3.5 ℃, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethylene glycol is 96.8%, but energy efficient is the 14.78KJ/mol dimethyl oxalate.
[embodiment 3]
Press Fig. 1, it is 2.5 meters that the oxalic acid diethyl ester hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Mg/SiO
2Catalyzer, in the weight of elemental copper, the consumption that is selected from the oxide compound of metallic copper and copper is that weight content is 40%, in the weight of simple substance magnesium, the oxide compound consumption that is selected from magnesium is that weight content is 0.1%.Heat-eliminating medium is a hydrogen.With temperature is that 25 ℃ hydrogen is introduced by cooling medium inlet, be diverted in each heat exchanging pipe, being equidirectional with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation simultaneously is warming up to 260 ℃, draw reactor through the heat-eliminating medium outlet then, enter in the mixer, with fresh hydrogen after the exterior tubing preheating that comes and oxalic acid diethyl ester weight percentage be 60% oxalic acid diethyl ester and alcohol mixture uniform mixing in mixing tank, the weight percentage that mixes the back oxalic acid diethyl ester is 60%, hydrogen and dimethyl oxalate mol ratio are 60: 1, temperature is 260 ℃, again in reactor is introduced in the reactor feedstocks import, with the outer copper containing catalyst contact reacts of tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 260 ℃, is that the weight space velocity of benchmark is 0.8hr with oxalic acid diethyl ester and alcoholic acid mixture weight
-1, hydrogen/ester mol ratio is 60: 1, reaction pressure is 6.0MPa.Under above structural parameter and condition, by the present invention the oxalic acid diethyl ester hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 5 ℃, the transformation efficiency of oxalic acid diethyl ester is 99.8%, the selectivity of ethylene glycol is 93.1%, but energy efficient is a 5.9KJ/mol hydrogen.
[embodiment 4]
Press Fig. 1, it is 3 meters that the oxalic acid diethyl ester hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Ba/SiO
2Catalyzer, in the weight of elemental copper, the consumption that is selected from the oxide compound of metallic copper and copper is that weight content is 50%, in the weight of simple substance barium, the consumption that is selected from barium metal is that weight content is 0.05%.Heat-eliminating medium is an oxalic acid diethyl ester.With temperature is that 80 ℃ oxalic acid diethyl ester is introduced by cooling medium inlet, be diverted in each heat exchanging pipe, being reverse direction with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation simultaneously is warming up to 180 ℃, draw reactor through the heat-eliminating medium outlet then, enter in the mixer, with fresh hydrogen after the exterior tubing preheating that comes and oxalic acid diethyl ester weight percentage be pure oxalic acid diethyl ester uniform mixing in mixing tank of 100%, the weight percentage that mixes the back oxalic acid diethyl ester is 100%, hydrogen and oxalic acid diethyl ester mol ratio are 180: 1, temperature is 180 ℃, again in reactor is introduced in the reactor feedstocks import, with the outer copper containing catalyst contact reacts of tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 180 ℃, and the weight space velocity that with the oxalic acid diethyl ester is benchmark is 0.1hr
-1, hydrogen/ester mol ratio is 180: 1, reaction pressure is 4.5MPa.Under above structural parameter and condition, by the present invention the oxalic acid diethyl ester hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 6 ℃, the transformation efficiency of oxalic acid diethyl ester is 100%, the selectivity of ethylene glycol is 94.5%, but energy efficient is the 24.7KJ/mol oxalic acid diethyl ester.
[embodiment 5]
Press Fig. 1, it is 3.5 meters that the dimethyl oxalate hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Cr/SiO
2Catalyzer, in the weight of elemental copper, the consumption that is selected from the oxide compound of metallic copper and copper is that weight content is 10%, in the weight of simple substance chromium, the consumption that is selected from the oxide compound of chromium is that weight content is 15%.Heat-eliminating medium is a methyl alcohol.With temperature is that 120 ℃ methyl alcohol is introduced by cooling medium inlet, be diverted in each heat exchanging pipe, being reverse direction with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation simultaneously is warming up to 210 ℃, draw reactor through the heat-eliminating medium outlet then, enter in the mixer, with fresh hydrogen after the exterior tubing preheating that comes and dimethyl oxalate weight percentage be pure dimethyl oxalate uniform mixing in mixing tank of 100%, the weight percentage that mixes the back dimethyl oxalate is 10%, the mol ratio of hydrogen and dimethyl oxalate is 200: 1, temperature is 210 ℃, again in reactor is introduced in the reactor feedstocks import, with the outer copper containing catalyst contact reacts of tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 210 ℃, is that the weight space velocity of benchmark is 5hr with dimethyl oxalate and methanol mixture weight
-1, hydrogen/ester mol ratio is 200: 1, reaction pressure is 1.8MPa.Under above structural parameter and condition, by the present invention the dimethyl oxalate hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 5 ℃, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethylene glycol is 94.2%, but energy efficient is a 10.9KJ/mol methyl alcohol.
[embodiment 6]
Press Fig. 1, it is 3.5 meters that the dimethyl oxalate hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Mn/SiO
2Catalyzer, in the weight of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 25%, in the weight of simple substance manganese, the consumption that is selected from the oxide compound of manganese is that weight content is 3%.Heat-eliminating medium is a dimethyl oxalate.Be that 200 ℃ dimethyl oxalate is introduced by cooling medium inlet and is diverted in each heat exchanging pipe with temperature, being reverse direction with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation simultaneously is warming up to 280 ℃, draw reactor through the heat-eliminating medium outlet then, enter in the mixer, with fresh hydrogen after the exterior tubing preheating that comes and dimethyl oxalate weight percentage be pure dimethyl oxalate uniform mixing in mixing tank of 100%, the weight percentage that mixes the back dimethyl oxalate is 100%, the mol ratio of hydrogen and dimethyl oxalate is 100: 1, temperature is 280 ℃, again in reactor is introduced in the reactor feedstocks import, with the outer copper containing catalyst contact reacts of tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 280 ℃, and the weight space velocity that with the dimethyl oxalate is benchmark is 0.25hr
-1, the hydrogen ester mol ratio is 100: 1, reaction pressure is 3.8MPa.Under above structural parameter and condition, by the present invention the dimethyl oxalate hydrogenation being produced glycol reaction designs, the same radial section temperature difference of its catalyst in reactor bed is less than 5 ℃, the transformation efficiency of dimethyl oxalate is 100%, the selectivity of ethylene glycol is 95.1%, but energy efficient is the 22.5KJ/mol dimethyl oxalate.
[embodiment 7]
Press Fig. 1, it is 3.5 meters that the oxalic acid diethyl ester hydrogenation is produced ethylene glycol calandria type fixed bed reactor internal diameter.Copper containing catalyst is Cu-Ca/SiO
2Catalyzer, in the weight of elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 32%, in the weight of simple substance calcium, the consumption that is selected from the oxide compound of calcium is that weight content is 0.5%.Heat-eliminating medium is an ethanol.With temperature is that 130 ℃ ethanol is introduced by cooling medium inlet, be diverted in each heat exchanging pipe, being equidirectional with the flow direction of raw material and solvent mixture flows, the reaction heat that absorbs the outer beds of tubulation simultaneously is warming up to 220 ℃, draw reactor through the heat-eliminating medium outlet then, enter in the mixer, with fresh hydrogen after the exterior tubing preheating that comes and oxalic acid diethyl ester weight percentage be pure oxalic acid diethyl ester uniform mixing in mixing tank of 100%, the weight percentage that mixes the back oxalic acid diethyl ester is 10%, hydrogen and oxalic acid diethyl ester mol ratio are 40: 1, temperature is 220 ℃, again in reactor is introduced in the reactor feedstocks import, with the outer copper containing catalyst contact reacts of tubulation, generate the reaction effluent that contains ethylene glycol.The operational condition of reactor is: temperature of reaction is 220 ℃, is that the weight space velocity of benchmark is 10hr with oxalic acid diethyl ester and alcoholic acid mixture weight
-1, hydrogen/ester mol ratio is 40: 1, reaction pressure is 2.5MPa.Under above structural parameter and condition, by the present invention the oxalic acid diethyl ester hydrogenation being produced glycol reaction designs, the same cross-section radial temperature difference of its catalyst in reactor bed is less than 5.5 ℃, the transformation efficiency of oxalic acid diethyl ester is 99.7%, the selectivity of ethylene glycol is 93.4%, but energy efficient is a 10KJ/mol ethanol.
[comparative example 1]
The structural parameter of catalyzer, condition, reaction raw materials and the fixed-bed reactor of certain dimethyl oxalate hydrogenation production ethylene glycol are identical with embodiment 1, and unique difference is that its inside reactor is not provided with heat exchanging pipe.The same cross-section radial temperature difference of its beds is less than 15 ℃, and the transformation efficiency of dimethyl oxalate is 95.8%, and the selectivity of ethylene glycol is 85.6%, not energy efficient.
[comparative example 2]
The structural parameter of catalyzer, condition, reaction raw materials and the fixed-bed reactor of certain oxalic acid diethyl ester hydrogenation production ethylene glycol are identical with embodiment 4, and unique difference is that its inside reactor is not provided with heat exchanging pipe.The same cross-section radial temperature difference of its beds is less than 18 ℃, and the transformation efficiency of oxalic acid diethyl ester is 94.6%, and the selectivity of ethylene glycol is 84.5%, not energy efficient.
Claims (6)
1. method with preparing ethylene glycol from oxalic ester, with barkite and hydrogen is raw material, the mol ratio of hydrogen and barkite is 40～200: 1, Fatty Alcohol(C12-C14 and C12-C18) with 1～4 carbon is a solvent, the weight percent of solvent and raw material medium-height grass acid esters is 0～0.9: 1, is heat-eliminating medium with at least a in barkite, hydrogen or the solvent, is 160 ℃～280 ℃ in temperature, pressure is 1.0～6.0MPa, is that the weight space velocity of benchmark is 0.1～10h with the mixture weight of barkite and solvent
-1Hydrogen/ester mol ratio is under 40～200: 1 the condition, pass through in the tubulation of heat-eliminating medium in the calandria type fixed bed reactor, beds is positioned at outside the tubulation, enter in the reactor behind heat-eliminating medium and fresh feed and the solvent mixture uniform mixing, the copper containing catalyst contact reacts outer with tubulation generates ethylene glycol, and wherein the flow direction of the flow direction of heat-eliminating medium and raw material and solvent mixture shows the same direction or opposite directions, the weight percentage of barkite 〉=10%.
2. the method with preparing ethylene glycol from oxalic ester according to claim 1, it is characterized in that the operational condition of reactor is: temperature of reaction is 180～260 ℃, is that the weight space velocity of benchmark is 0.1～6h with the mixture weight of barkite and solvent
-1, hydrogen/ester mol ratio is 60～180: 1, and reaction pressure is 1.5～6.0MPa, and the weight percentage of barkite is 10～100%.
3. the method with preparing ethylene glycol from oxalic ester according to claim 1, when it is characterized in that described barkite is dimethyl oxalate, solvent is a methyl alcohol.
4. the method with preparing ethylene glycol from oxalic ester according to claim 1, when it is characterized in that described barkite is oxalic acid diethyl ester, solvent is an ethanol.
5. the method with preparing ethylene glycol from oxalic ester according to claim 1, it is characterized in that copper containing catalyst is with silicon oxide, aluminum oxide, at least a in the molecular sieve is carrier, active ingredient is selected from metallic copper, the oxide compound of copper or its mixture, auxiliary agent is selected from zinc, barium, magnesium, at least a in the oxide compound of manganese or chromium metal or its metal, with the carrier is benchmark, weight in elemental copper, be selected from metallic copper, the oxide compound of copper or the consumption of its mixture are that weight content is 5%～50%, in the weight of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal or promoter metal is that weight content is 0.05～15%.
6. the method with preparing ethylene glycol from oxalic ester according to claim 5, it is characterized in that copper containing catalyst is carrier with the silicon oxide, active ingredient is selected from the oxide compound of copper, auxiliary agent is selected from least a in the oxide compound of the oxide compound of oxide compound, barium of zinc or chromium, with the carrier is benchmark, weight in elemental copper, the consumption that is selected from the oxide compound of copper is that weight content is 10%～35%, in the weight of auxiliary agent elemental metals, the consumption that is selected from the oxide compound of promoter metal is that weight content is 0.1～5%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103585933A (en) * | 2013-11-25 | 2014-02-19 | 南京国昌化工科技有限公司 | Corrugated board type uniform-temperature hydrogenation reactor |
| CN104841339A (en) * | 2015-04-16 | 2015-08-19 | 中国五环工程有限公司 | Novel hydrogenation reactor for synthesis gas-to-ethylene glycol process |
| CN107848921A (en) * | 2015-07-29 | 2018-03-27 | 巴斯夫欧洲公司 | Method for producing monoethylene glycol |
| CN108017511A (en) * | 2017-08-04 | 2018-05-11 | 华东理工大学 | A kind of method of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol |
| CN110624480A (en) * | 2018-06-22 | 2019-12-31 | 中国石油化工股份有限公司 | Fixed bed reactor and unsaturated light hydrocarbon hydrogenation method |
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| DE4207905A1 (en) * | 1992-03-12 | 1993-09-16 | Bayer Ag | FIXED BED REACTORS WITH SHORT CATALYST BED IN FLOW DIRECTION |
| CN101475442B (en) * | 2008-12-18 | 2011-11-30 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101475441B (en) * | 2008-12-18 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103585933A (en) * | 2013-11-25 | 2014-02-19 | 南京国昌化工科技有限公司 | Corrugated board type uniform-temperature hydrogenation reactor |
| CN104841339A (en) * | 2015-04-16 | 2015-08-19 | 中国五环工程有限公司 | Novel hydrogenation reactor for synthesis gas-to-ethylene glycol process |
| CN107848921A (en) * | 2015-07-29 | 2018-03-27 | 巴斯夫欧洲公司 | Method for producing monoethylene glycol |
| CN107848921B (en) * | 2015-07-29 | 2022-01-25 | 巴斯夫欧洲公司 | Process for the production of monoethylene glycol |
| CN108017511A (en) * | 2017-08-04 | 2018-05-11 | 华东理工大学 | A kind of method of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol |
| CN110624480A (en) * | 2018-06-22 | 2019-12-31 | 中国石油化工股份有限公司 | Fixed bed reactor and unsaturated light hydrocarbon hydrogenation method |
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