Background technology
Ethylene glycol is a kind of important industrial chemicals, it and terephthaldehyde's acid reaction generate PETG, can be used as the raw material of polyester fiber and polyester plastics, also be widely used in producing the industrial circles such as lubricant, plasticizer, paint, adhesive, surfactant, explosive, also can be used for configuring anti-icing fluid or being directly used as organic solvent simultaneously.In addition, also can be applicable to the industries such as coating, soup, brake-fluid and ink.
Current industrial being produced ethylene glycol mainly adopts oil ethene to obtain oxirane through gaseous oxidation, then through the route of liquid-phase catalysis hydration preparing ethylene glycol.China's oil inadequate resource, producing ethylene by cracking fuel consumption is large, and ethene is also the raw material of many staple products, and the ethylene glycol breach of China was increasing in recent years.Increasingly reduce and the energy general layout of " rich coal, weak breath, oil-poor " from China's oil resource, technology the supplementing as petroleum path of Development of Coal gas making synthesizing glycol, has important practical significance and long-range strategic importance in China.
Coal gas is produced in all multi-routes of ethylene glycol the most deep through the research of oxalate hydrogenation method with carbon monoxide, produce and carry out in two steps, first adopt CO synthesis of oxalic ester by gaseous catalysis, ethylene glycol is obtained again by oxalate hydrogenation, existing commerical test plant running, has heavy industrialization prospect at present.In the technology path of oxalate preparing ethylene glycol, relate to three kinds of crucial catalyst, wherein selective dehydrogenation catalyst, oxalate synthesis catalyst and oxalate hydrogenation catalyst in high-load CO source of the gas, what the applicant applied for is the third catalyst-hydrogenation of oxalate for preparing ethylene glycol catalyst.
Since 20 world seventies, the existing a lot of report of oxalate hydrogenation process.Domestic, Fujian structure of matter research institute adopts Cu-Cr series catalysts to carry out the model study of diethy-aceto oxalate hydrogenation, reaction temperature (208 ~ 230) DEG C, pressure (2.5 ~ 3.0) MPa, under gas liquid ratio 46 ~ 60 condition, the average conversion 99.8% of diethy-aceto oxalate on catalyst, ethylene glycol average selectivity 95.3%, catalyst runs 1134h performance is without obvious decline.East China University of Science adopts CuSi series catalysts to investigate dimethyl oxalate (DMO) Hydrogenation ethylene glycol (EG) process, it utilizes ammoniacal liquor, urea etc. to prepare multiple CuSi catalyst as precipitating reagent co-precipitation, majority be reported in 190-205 DEG C, 3.0MPa, hydrogen ester than 80, liquid air speed 1.0g g
cath
-1under condition, dimethyl oxalate conversion ratio about 95%, glycol selectivity about 90%.Fudan University, Xiamen University and University Of Tianjin all utilize the method for ammonia still process to develop multiple CuSi series catalysts, the better level of catalyst of bibliographical information be 190-200 DEG C, 2.5-3.0MPa, hydrogen ester is than under the reaction condition of 50-80, DMO conversion ratio about 99%, EG yield more than 90%.
More with the research of Ube company abroad, fine man of virtue and ability of Miyazaki of the said firm etc. has successively applied for the catalyst patent of 7 hydrogenation of oxalate for preparing ethylene glycol in nineteen eighty-two, compares multiple different carriers, finally with the SiO of co-precipitation in ZL57-122938
2best; ZL57-122939, ZL57-122940, ZL57-122941 all adopt precipitation method Kaolinite Preparation of Catalyst, and precipitating reagent has ammoniacal liquor, NaOH, (NH respectively
4)
2cO
3deng; ZL57-122946, adopts infusion process to prepare Cu/TiO
2hydrogenation catalyst, but EG is selective relatively poor, only (70 ~ 80) %; ZL57-180432 adopts thermal precipitation gel method to prepare CuSi hydrogenation catalyst, and time active best (190 ~ 210) DEG C, EG is selective reaches 99%; ZL57-123127 describes and adopts the CuCrMn for preparing of coprecipitation without Si System Catalyst.The above-mentioned patent of performance improving CuSi hydrogenation catalyst by adding various auxiliary agent also has report, all have employed and introduce the methods such as auxiliary agent such as Zn, La, Mo, Ba, Mn in coprecipitation process, but whether auxiliary agent has in significant facilitation patent and do not clearly state.
The UCC of the U.S. also applied for two patents in 1985, and US4677234 is the technique patent of gas phase catalyst hydrogenation synthesizing of ethylene glycol, but mentioned the CuSi hydrogenation catalyst prepared for raw material with copper carbonate and ammonium carbonate in patent; US4628128 then describes Cu/SiO prepared by a kind of infusion process
2hydrogenation catalyst.Gondola ARCO also applied for a hydrogenation catalyst patent US4112245 in 1976, in this patent, catalyst is copper chromium system prepared by coprecipitation, they think that hydrogenation catalyst preferably selects Cu-Zn-Cr or Cu-Cr system, and Ca, Ba etc. may improve the hydrogenation activity of catalyst.
Hydrogenation of Dimethyl Oxalate catalyst mainly contains the large system of CuSi and CuCr two, although the latter's superior activity, pollutes large, Cr severe toxicity, harmful.At present, domestic industry or pilot-plant major part have employed CuSi series hydrocatalyst, and catalyst have employed the preparation of the sluggish precipitation such as ammonia still process or hydrolysis of urea substantially, the activity and selectivity of catalyst can ensure commercial Application substantially, but the ammoniacal liquor used in catalyst preparation process and urea all can generate a large amount of ammonia, bring certain pollution to the production environment of catalyst; And using CuSi series catalysts prepared by NaOH and copper nitrate and Ludox co-precipitation, selective and yield also has gap.
Summary of the invention
Technical problem to be solved of the present invention is that the ammoniacal liquor that uses in Hydrogenation of Dimethyl Oxalate catalyst preparation process and urea all can generate a large amount of ammonia, bring certain pollution to the production environment of catalyst, a kind of Catalysts and its preparation method and the application with the oxalic ester hydrogenation synthesizing of ethylene glycol of high activity, high selectivity and longer life are provided.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
Mix an oxalate hydrogenation catalyst for silicon source method synthesis, described catalyst composition is expressed as CuO-M
xo
y-SiO
2, copper is main active component, M
xo
yfor B
2o
3, ZrO
2, MnO
2, Fe
2o
3, ZnO, Al
2o
3, CeO
2, B
2o
3or Ga
2o
3in one, between each component, mass percent is: CuO:M
xo
y: SiO
2%:(0.1 ~ 5 ,=(10 ~ 40)) %:(60 ~ 90) %.
Mix a preparation method for the oxalate hydrogenation catalyst of silicon source method synthesis, comprise the following steps:
(1) according to measuring than taking soluble copper salt and builder salts, be mixed with mixed solution, wherein the concentration of mantoquita is 0.1 ~ 1.5mol/L;
(2) added in Ludox by a certain amount of dust technology and be configured to acidic silicasol solution, adjust ph is 1 ~ 2;
(3), in the mixed solution prepared by Ludox instillation step (1) in step (2) under room temperature intense agitation, stirring 1 ~ 7 hour is continued;
(4) sodium silicate aqueous solution is instilled the mixed system in step (3), after stirring at room temperature 2 ~ 6h, crystallization 12 ~ 24h in 100 ~ 130 DEG C of water heating kettles;
(5) solid that step (4) obtains is carried out successively wash, alcohol wash, then dry at 80 ~ 120 DEG C;
(6) by solid roasting 3 ~ 8 hours obtained oxalate hydrogenation catalysts at 300 ~ 600 DEG C after oven dry.
Soluble copper salt in described step (1) is the nitrate of copper, acetate or halide.
Builder salts in described step (1) is selected from one in nitrate corresponding to Zr, Mn, Fe, Zn, Al, Ce, Ga, acetate or halide or builder salts is boric acid.
With SiO
2meter, the ratio of the sodium silicate solution in the silicon sol solution in described step (3) and step (4) is 1:4 ~ 4:1.
In described step (3), silicon sol solution rate of addition is 1 ~ 20mL/min.
Described step (4) mesosilicic acid sodium solution dropwises in 0.5 ~ 1h.
Catalyst needs compression molding before using, and is crushed to 40 ~ 60 orders after the catalyst compressing tablet after roasting.Catalyst needs with pure hydrogen reduction 2 ~ 12 hours before using, and reduction temperature is 220 ~ 350 DEG C.Pure hydrogen is passed into after reduction terminates, the oxalate methanol solution of 5 ~ 15wt% enters reactor after vaporizer vaporization also preheating, reaction temperature be 190 ~ 240 DEG C, reaction pressure carries out reaction generating glycol with hydrogen under being 2.0 ~ 3.0MPa condition, oxalate mass space velocity is 0.1 ~ 1h
-1, hydrogen ester ratio is 50 ~ 100.Oxalate can be selected from dimethyl oxalate or diethy-aceto oxalate.
Beneficial effect of the present invention: (1) present invention employs the method in Ludox and sodium metasilicate mixing silicon source, Ludox, sodium metasilicate is utilized to be hydrolyzed the hydroxyl of generation and between copper and auxiliary agent, to form stable chemical constitution, utilize the cooperative effect between two kinds of silicon sources to increase the hydrogenation activity of catalyst and selective simultaneously, also enhance the anti-caking power of copper catalyst simultaneously.(2) sodium metasilicate had both served as part silicon source, serve the effect of precipitating reagent simultaneously, avoid and use volatile precipitating reagent, not only improve the environment in catalyst preparation process, and the catalyst performance of preparation can reach or completely slightly above the catalyst in above-mentioned patent.(3) this catalyst has higher activity and selectivity to hydrogenation of oxalate for preparing ethylene glycol reaction, and oxalate conversion ratio is greater than 99%, and glycol selectivity is greater than 95%.
Detailed description of the invention
Below by the reactivity worth of forming method and catalysis oxalic ester hydrogenation synthesizing of ethylene glycol thereof that the catalyst related in the present invention is described by specific embodiment, but scope of the present invention is not limited to these embodiments.
Embodiment 1
The preparation method of the oxalate hydrogenation catalyst of the mixing silicon source method synthesis of the present embodiment is as follows:
With 100g catalyst gauge, according to 32%CuO, 1%B
2o
3, 67%SiO
2ratio takes Gerhardite 96.64g and boric acid 1.78g and adds in 1200mL water, heating is stirred to solid and all dissolves, 134g content 25% Ludox (pH is 1) after nitric acid acidifying is dropwise added and joined in solution, and strong stirring 7h, then instilled in mixed system by the aqueous solution containing 68.12g sodium metasilicate, wherein the ratio of Ludox and sodium metasilicate is that 1:1(is with SiO
2meter), to stir after 2h crystallization 12h in 130 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 120 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: getting 40 ~ 60 object particles by sieving after the catalyst breakage prepared, being filled in fixed bed reactors, and with after hydrogen reducing 4h at 350 DEG C, at 205 DEG C, pressure 2.5MPa, hydrogen ester mol ratio 67, liquid hourly space velocity (LHSV) 1.0 g g
cath
-1under carry out dimethyl oxalate catalytic hydrogenation reaction for preparing glycol.Gather reactant after 8h is carried out in reaction and carry out gas chromatographic analysis, the results are shown in Table 1.
Embodiment 2
The preparation method of the oxalate hydrogenation catalyst of the mixing silicon source method synthesis of the present embodiment is as follows:
With 100g catalyst gauge, according to 20%CuO, 0.5%ZnO, 79.5%SiO
2getting Gerhardite 60.4g and zinc nitrate hexahydrate 1.83g adds in 2500mL water, the concentration of mantoquita is 0.1mol/L, be stirred to solid all to dissolve, the Ludox (pH is 2) of the 212g content 25% after nitric acid acidifying is dropwise added and joined in solution, and strong stirring 1h, then instilled in mixed system by the aqueous solution containing 53.89g sodium metasilicate, wherein the ratio of Ludox and sodium metasilicate is that 2:1(is with SiO
2meter), to stir after 2h crystallization 20h in 110 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 100 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: catalyst reduction adopts 300 DEG C, reacts 210 DEG C, pressure 2MPa, hydrogen ester than 60, liquid hourly space velocity (LHSV) 0.6 g g
cath
-1, the other the same as in Example 1, the results are shown in Table 1.
Embodiment 3
The preparation method of the oxalate hydrogenation catalyst of the mixing silicon source method synthesis of the present embodiment is as follows:
With 100g catalyst gauge, according to 20%CuO, 0.1%Al
2o
3, 79.9%SiO
2getting Gerhardite 60.4g and ANN aluminium nitrate nonahydrate 0.37g adds in 167mL water, the concentration of mantoquita is 1.5mol/L, be stirred to solid all to dissolve, the Ludox (pH is 2) of the 106.53g content 25% after nitric acid acidifying is dropwise added and joined in solution, and strong stirring 6h, then instilled in mixed system by the aqueous solution containing 108.3g sodium metasilicate, wherein the ratio of Ludox and sodium metasilicate is that 1:2(is with SiO
2meter), to stir after 4h crystallization 15h in 120 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 90 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: catalyst reduction adopts 250 DEG C, reacts 225 DEG C, pressure 2.1MPa, hydrogen ester than 80, liquid hourly space velocity (LHSV) 0.8 g g
cath
-1, the other the same as in Example 1, the results are shown in Table 1.
Embodiment 4
The preparation method of the oxalate hydrogenation catalyst of the mixing silicon source method synthesis of the present embodiment is as follows:
With 100g catalyst gauge, according to 28%CuO, 2%ZrO
2, 70%SiO
2get Gerhardite and five nitric hydrate zirconiums add in 1500mL water, be stirred to solid all to dissolve, Ludox (pH is 1.5) after nitric acid acidifying is dropwise added and joined in solution, and strong stirring 4h, then instill in mixed system by sodium silicate solution, wherein the ratio of Ludox and sodium metasilicate is that 1:3(is with SiO
2meter), to stir after 6h crystallization 14h in 130 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 110 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: catalyst reduction adopts 290 DEG C, reacts 190 DEG C, pressure 2MPa, hydrogen ester than 90, liquid hourly space velocity (LHSV) 0.5 g g
cath
-1, the other the same as in Example 1, the results are shown in Table 1.
Embodiment 5
The preparation method of the oxalate hydrogenation catalyst of the mixing silicon source method synthesis of the present embodiment is as follows:
With 100g catalyst gauge, according to 20%CuO, 5%MnO
2, 75%SiO
2get Gerhardite and four nitric hydrate manganese add in 800mL water, wherein the concentration of mantoquita is 0.3125mol/L, be stirred to solid all to dissolve, Ludox (pH is 1) after nitric acid acidifying is dropwise added and joined in solution, and strong stirring 4h, then instill in mixed system by sodium silicate solution, wherein the ratio of Ludox and sodium metasilicate is that 1:4(is with SiO
2meter), to stir after 4h crystallization 18h in 100 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 120 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: catalyst reduction adopts 260 DEG C, reacts 200 DEG C, pressure 2MPa, hydrogen ester than 50, liquid hourly space velocity (LHSV) 0.4 g g
cath
-1, the other the same as in Example 1, the results are shown in Table 1.
Embodiment 6
The preparation method of the oxalate hydrogenation catalyst of the mixing silicon source method synthesis of the present embodiment is as follows:
With 100g catalyst gauge, according to 39.9%CuO, 0.1%CeO
2, 60%SiO
2get Gerhardite and six nitric hydrate ceriums add in 900mL water, be stirred to solid all to dissolve, Ludox (pH is 2) after nitric acid acidifying is dropwise added and joined in solution, and strong stirring 4h, then being instilled in mixed system by sodium silicate aqueous solution and being adjusted to PH is 12, and wherein the ratio of Ludox and sodium metasilicate is that 3:2(is with SiO
2meter), to stir after 2h crystallization 24h in 130 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 80 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: catalyst reduction adopts 230 DEG C, reacts 210 DEG C, pressure 2MPa, hydrogen ester than 60, liquid hourly space velocity (LHSV) 1.0 g g
cath
-1, the other the same as in Example 1, the results are shown in Table 1.
Embodiment 7
The preparation method of the oxalate hydrogenation catalyst of the mixing silicon source method synthesis of the present embodiment is as follows:
With 100g catalyst gauge, according to 25%CuO, 0.8%Ga
2o
3, 74.2%SiO
2get Gerhardite and nine nitric hydrate galliums add in 3000mL water, be stirred to solid all to dissolve, Ludox (pH is 1.5) after nitric acid acidifying is dropwise added and joined in solution, and strong stirring 4h, then instill in mixed system by sodium silicate solution, wherein the ratio of Ludox and sodium metasilicate is that 3:1(is with SiO
2meter), to stir after 6h crystallization 15h in 130 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 120 DEG C, stand-by at catalyst obtained after 600 DEG C of roasting 3h.
Evaluating catalyst: catalyst reduction adopts 280 DEG C, reacts 205 DEG C, pressure 3MPa, hydrogen ester than 70, liquid hourly space velocity (LHSV) 0.7 g g
cath
-1, the other the same as in Example 1, the results are shown in Table 1.
Embodiment 8
The preparation method of the oxalate hydrogenation catalyst of the mixing silicon source method synthesis of the present embodiment is as follows:
With 100g catalyst gauge, according to 10%CuO, 1%Fe
2o
3, 89%SiO
2get Gerhardite and Fe(NO3)39H2O adds in 200mL water, be stirred to solid all to dissolve, Ludox (pH is 1) after nitric acid acidifying is dropwise added and joined in solution, and strong stirring 4h, then instilled in mixed system by sodium silicate solution and be adjusted to PH12, wherein the ratio of Ludox and sodium metasilicate is that 4:1(is with SiO
2meter), to stir after 2h crystallization 24h in 110 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 120 DEG C, stand-by at catalyst obtained after 300 DEG C of roasting 8h.
Evaluating catalyst: catalyst reduction adopts 320 DEG C, reacts 220 DEG C, pressure 2.5MPa, hydrogen ester than 80, liquid hourly space velocity (LHSV) 0.4 g g
cath
-1, the other the same as in Example 1, the results are shown in Table 1.
Reference examples 1
Catalyst preparing: silicon source all from Ludox, the other the same as in Example 1.
Evaluating catalyst: with embodiment 1.
Reference examples 2
Catalyst preparing: silicon source all from sodium metasilicate, the other the same as in Example 1.
Evaluating catalyst: with embodiment 1.
Reference examples 3
Catalyst preparing: with 100g catalyst gauge, according to 32%CuO, 68%SiO
2ratio takes Gerhardite and adds in 1200mL water, heating is stirred to solid and all dissolves, Ludox (pH1) after nitric acid acidifying is dropwise added in joined solution, and strong stirring 7h, then instill in mixed system by sodium silicate solution, wherein the ratio of Ludox and sodium metasilicate is that 1:1(is with SiO
2meter), to stir after 2h crystallization 24h in 130 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 120 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: with embodiment 1.
Reference examples 4
Catalyst preparing: with 100g catalyst gauge, according to 32%Cu, 1%B
2o
3, 68%SiO
2ratio takes Gerhardite and boric acid adds in 1200mL water, heating is stirred to solid and all dissolves, the ammoniacal liquor being 25% by concentration (ammonia and copper mol ratio are about 7.5:1) dropwise adds and is joined in solution, to generate precipitation dissolve completely after dropwise add Ludox and after strong stirring 0.5h at 90 DEG C ammonia still process 3-6h be about 6.5 to system pH, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dry at 120 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: with embodiment 1.
Reference examples 5
Catalyst preparing: with 100g catalyst gauge, according to 32%CuO, 68%SiO
2ratio takes copper nitrate and adds in 1200mL water, heating is stirred to solid and all dissolves, Ludox (Ph1) after nitric acid acidifying is dropwise added in joined solution, and strong stirring 7h, then instilling in mixed system by sodium hydroxide solution, is 8 to Ph value, to stir after 2h crystallization 24h in 130 DEG C of water heating kettles, the solidliquid mixture obtained carries out centrifugal washing, alcohol wash successively, and then dries at 120 DEG C, stand-by at catalyst obtained after 450 DEG C of roasting 6h.
Evaluating catalyst: with embodiment 1.
The evaluation result of the catalyst that each embodiment obtains is as shown in table 1.
Table 1 catalyst composition and evaluation result
As shown in Table 1, according to the catalyst that the inventive method prepares, DMO conversion ratio and EG is selective significantly improves, in comparative example except the standby catalyst performance of ammonia still process legal system and catalyst of the present invention quite except, all the other all have obvious gap, illustrate that the method for preparing catalyst in this patent can reach the requirement of application completely, and preparation environmental friendliness, pollution-free, meet green chemical concept.