CN104772153A - Preparation method and applications of steel slag-based metal oxide solid base catalyst - Google Patents
Preparation method and applications of steel slag-based metal oxide solid base catalyst Download PDFInfo
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- CN104772153A CN104772153A CN201410013329.1A CN201410013329A CN104772153A CN 104772153 A CN104772153 A CN 104772153A CN 201410013329 A CN201410013329 A CN 201410013329A CN 104772153 A CN104772153 A CN 104772153A
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Abstract
The present invention discloses a preparation method and applications of a steel slag-based metal oxide solid base catalyst, wherein steel slag being rich in magnesium, calcium, aluminum, iron and other metal elements is adopted as a raw material, inorganic acid is adopted to dissolve, the filtrate is subjected to precipitant titration, precipitation aging, filtration, drying and calcining activating to prepare the steel slag-based metal oxide solid base catalyst, and the steel slag-based metal oxide solid base catalyst is used for the diethyl carbonate preparation reaction through the reaction of urea or urethane and ethanol. According to the present invention, the steel slag solid waste is utilized to prepare the multi-metal oxide solid base catalyst, the preparation process is simple and practical, and the catalyst cost can be effectively reduced, and the obtained product as the alternative solid base has the broad application prospects; and the catalyst provides the excellent catalysis activity for synthesis of the high added value fine chemical diethyl carbonate, has advantages of environmental protection, no corrosion, no pollution and the like, and is easily subjected to industrial applications.
Description
Technical field
The invention belongs to metal oxide catalyst Synthesis and applications field, particularly prepared from steel slag is for the method for solid basic catalyst, and the application in urea or the reaction of urethanes alcoholysis synthesizing diethyl carbonate.
Background technology
Slag is the using industrial solid waste produced in steelmaking process, and discharge rate is about the 8-20% of crude steel output, and the annual slag output in the whole world surpasses 500,000,000 tons, and China is annual produces 7,000 ten thousand tons of slags, but its utilization rate only has 10%.At present, slag, mainly as pavement material, backfilling material, slag cement, sintering deposit raw material etc., belongs to low value-added Land use models.All the other most of slags, as discarded object, not only take good farmland, also bring Heavy environmental pollution.It is reported, the slag accumulating amount of China's accumulation has surpassed more than 200,000,000 ton, and along with the continuous increase of output of steel, accumulating amount is increasing.In today that environmental protection and resource circulation utilization come into one's own day by day, the recycling of steel slag resource, especially its high value added utilization has important research and utilization value.On the other hand, be rich in alkali metal or the transiting metal components such as calcium, magnesium, aluminium, iron, manganese in slag, the metal oxide solid base catalyst containing Determination of multiple metal elements can be prepared.Due to the cost that slag itself is cheap, the present invention substitutes in conventional alkaline catalyst at slag based solid alkali catalyst and has broad application prospects.In view of the foregoing, effectively utilize abundant steel slag resource prepare high value added product for the sustainable development of economic society significant and practical value.
Diethyl carbonate is a kind of important organic synthesis intermediate, has extensive use in fields such as solvent, electrolyte, organic synthesis, pharmacy and engineering plastics.The synthetic method of the diethyl carbonate of current report mainly comprises: phosgenation, ester-interchange method, oxidation of ethanol carbonylation method, alcoholysis of urea etc.In recent years, the direct alcoholysis method of urea, or urethanes is prepared in the first alcoholysis of urea, then prepare diethyl carbonate with ethanol synthesis.Because raw material urea and ethanol are large cheap chemicals, cheap and easy to get, and in course of reaction, do not relate to generation and the discharge of poisonous and harmful substance, between product, boiling point difference is comparatively large, is separated simple.There is activity lower (H.An, et.al., Appl.Catal.A433 – 434 (2012) 229 – 235.) in the catalyst Z nO-PbO of current report, DEC yield is lower than 21%, and catalyst activity component easily runs off, the unfavorable factors such as less stable, limit its practical application.Therefore, from industrial application value and practicality, develop the inexpensive and catalyst of efficient stable, for the route of synthesis fine chemicals diethyl carbonate, there is good development prospect.
Analyze in conjunction with above, utilize prepared from steel slag for activity solid base catalyst, and be applied to the synthesis of diethyl carbonate, significant for recycling with Green Chemical Engineering Process exploitation of resource.But not yet there is pertinent literature to report at present.
Summary of the invention
Technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, and object is to provide a kind of slag based solid alkali method for preparing catalyst and the application in diethyl carbonate synthesis thereof.This catalyst preparation process is simple and practical, with low cost, can be used to the solid base catalyst preparing low cost, is expected to realize effectively substituting of solid base catalyst; And this catalyst has excellent catalytic activity, can be used for the process that diethyl carbonate prepared by urea or urethanes and ethanol synthesis.
In order to achieve the above object, the present invention takes following technical scheme:
Slag metal oxides Catalysts and its preparation method, catalyst raw material derives from slag, its preparation process comprise the steps: slag powder under agitation in certain density inorganic acid fluid dissolution of metals be corresponding saline solution, above-mentioned inorganic acid concentration scope is 1mol/L to 12mol/L, and the quality of slag and inorganic acid solution is 1:5 to 1:50 than scope slag/hydrochloric acid solution.Above-mentioned slag powder diameter is less than the particle of 3mm, and advantage is that small particle diameter slag is conducive to acid solution rapid solution metallic element wherein, sandwiches slag micro powder, reach the object effectively utilizing slag raw material when reducing silicon polymerization.Fully dissolve on the basis of slag under aforementioned room temperature, be warming up to 80-120 DEG C under stirring condition, heating makes wherein silicon species polymerization, crosses and filters polymerization silicon species.Gained filtrate is titrated to pH=8-13 through alkaline precipitating agent, generates solid sediment, and in 20-100 DEG C of ageing.After filtration, distilled water washs solid sediment, dry, obtains catalyst precursor.Gained catalyst precursor, through calcination activation, obtains poly-metal deoxide solid base catalyst.Its composition depends on slag presoma used, and mainly containing magnesium, iron, aluminium, calcium, chlorine, after normalization method calculates, account for more than the 90wt% of gross mass in oxide and chlorine form, surplus is the micro constitutent such as manganese, titanium.
Described slag is selected from one or more mixtures in vessel slag, open hearth slag, electroslag.
Described inorganic acid is selected from one or more mixtures in hydrochloric acid, sulfuric acid, nitric acid, concentration 0.1-10mol/L.
Described precipitating reagent is selected from one or more mixtures in sodium carbonate, potash, NaOH, potassium hydroxide, ammoniacal liquor, urea, potassium phosphate, sodium phosphate, concentration 0.5-12mol/L.
Described catalyst calcination atmosphere is selected from air, nitrogen, argon gas, vacuum, preferred air, nitrogen.
Described catalyst sintering temperature 200-1200 DEG C, preferably 300 DEG C-900 DEG C, preferably 300 DEG C-600 DEG C further.
The diethyl carbonate that is applied to of described slag metal oxides catalyst synthesizes, reaction is carried out as follows: in stainless steel cauldron, add urea or urethanes, above-mentioned catalyst and ethanol, after closed reactor, be warming up to reaction temperature, react certain hour at autogenous pressures, in process, produce ammonia.After question response terminates, obtain the mixed liquor containing the product such as unconverted raw material and diethyl carbonate.
Above-mentioned catalyst amount is the 0.01wt%-5wt% based on reactant liquor gross mass, preferred 0.05wt%-2wt%.
Molar ratio range ethanol/urea (the urethanes)=2-20 of above-mentioned ethanol and urea or urethanes, preferred 4-12; Reaction temperature 160 DEG C-220 DEG C, preferably 180 DEG C-210 DEG C; Reaction time is 0.1h-5h, preferred 1h-3h.
The present invention compared with prior art has following beneficial effect:
(1) utilize prepared from steel slag for solid base catalyst, achieve industrial solid castoff Comprehensive Utilization of Steel Slag and utilize preparation high added value catalysis material;
(2) method for preparing catalyst is simple and practical, and prepared solid base catalyst has 150m
2/ g-400m
2/ g high specific surface area and 1-20nm larger aperture.
(3) above-mentioned catalyst prepares in diethyl carbonate process the catalytic performance and repeat performance with excellence at urea/urethanes and ethanol, diethyl carbonate yield higher than 27%, catalyst repeatedly after be still substantially kept above 26% diethyl carbonate yield.
Accompanying drawing explanation
Fig. 1 is catalyst nitrogen Adsorption and desorption isotherms;
Fig. 2 is the graph of pore diameter distribution of catalyst;
Fig. 3 is that catalyst XRD prepared by different preparation method schemes;
Fig. 4 is 450 degree of calcined catalyst (SN-450) CO
2-TPD schemes;
Fig. 5 is SN-450 catalyst repeat performance.
Detailed description of the invention
The present invention is introduced in detail below in conjunction with drawings and the specific embodiments.But following embodiment is only limitted to explain the present invention, and protection scope of the present invention should comprise the full content of claim, is not limited only to the present embodiment.And the present invention is by embodiment below, those skilled in the art can realize all the elements that the claims in the present invention record completely.
Embodiment 1
The preparation of slag based solid alkali catalyst: get 20g slag, be dissolved in 3mol/L aqueous hydrochloric acid solution, under the intense agitation of stir speed (S.S.) 100-500rpm, dissolved solution, under 90 DEG C of conditions, continue stirring 2 hours afterwards, in slag, institute's containing metal oxide or its compound dissolve substantially, and in slag, silicon species major part is suspended in solution with polymeric form simultaneously, cross and filter suspension, obtain yellow green filtrate.2mol/L NaOH solution dropwise instills this filtrate as precipitating reagent, and pH meter monitoring titration process, when pH reaches 10.5, reaches titration end-point.Stir 1 hour under continuing at this temperature, 80 DEG C of aged overnight.After filtration, deionized water washing is to close neutral, and 100 DEG C of dried overnight, obtain light tan solid, and in 350-650 DEG C of roasting 3 hours, obtain the catalyst after activation, be labeled as SN-T, wherein T represented sintering temperature for precipitation.
Nitrogen Adsorption and desorption isotherms and the graph of pore diameter distribution of sample is respectively by Fig. 1 and Fig. 2.Gained sample measures specific surface, pore-size distribution through low-temperature nitrogen adsorption method, analytical instrument AUTOSORB-1-C-TCD used, and sample, through 300 degree of pre-degassed 3h, removes the small-molecule substances such as physical absorption water.Wherein Fig. 1 nitrogen Adsorption and desorption isotherms abscissa is relative pressure P/P
0, be dimensionless number, P represents the absolute pressure of test point place nitrogen, P
0for the saturated vapour pressure of nitrogen under probe temperature.Ordinate is nitrogen adsorption amount, and unit is cm
3/ g, represents the amount of the adsorbate that unit adsorbent adsorbs under equilibrium temperature and pressure when balancing.Fig. 2 pore size distribution curve abscissa is pore size, and unit is dust
ordinate is specific pore volume, and represent that pore volume is to the differential in aperture, unit is
as can be seen from above-mentioned two figure, gained catalyst aperture meets IV type absorption isotherm in IUPAC standard, have obvious meso pore characteristics, and pore size distribution curve show sample pore-size distribution is narrower, is substantially in 2-15nm scope.
XRD analysis result in Fig. 3, adopts XRD analysis sample crystalline structure, instrument Empyrean, Cu-K alpha ray
analytic angle 2 θ scope 5 – 90o, step-length 0.013o.Under Fig. 3 shows different condition, Kaolinite Preparation of Catalyst is mainly containing Emission in Cubic MgO crystalline phase (JCPDS01-077-2179), and increase with sintering temperature, sample crystallinity strengthens to some extent, but peak shape still comparatively disperse, degree of crystallinity is poor.
Fig. 4 is CO
2temperature programmed desorption result, adopts CO
2temperature programmed desorption characterizes catalyst surface alkalescence, adopts AutoChem II2920 to analyze, thermal conductivity detector (TCD) (TCD), carrier gas helium flow velocity 30ml/min, spends, heating rate 10 DEG C/min from room temperature through temperature programming to 700.Fig. 4 abscissa is desorption temperature, and unit is degree (DEG C), and ordinate is CO
2desorption rate, unit is a μm ol CO
2/ g
catalyst.Can find out, 450 DEG C of calcined catalyst SN-450 have gentle high temperature CO significantly
2desorption peaks, quantitative result shows that sample basic sites total amount is 2055 μm of ol CO
2/ g, illustrates that this catalyst contains abundant basic sites.The above results shows that the method can prepare the solid base catalyst having and enrich basic sites.
The chemical composition of X-ray fluorescence method (XRF) working sample, analytical instrument AXIOS, sample is through adding boric acid binding agent compressing tablet post analysis, data acquisition normalized.
Slag and catalyst characterize through XRF elementary analysis and nitrogen adsorption, and result is as shown in the table:
The above results shows, slag major metal component is magnesium, calcium, iron, aluminium etc.After the preparation process such as acid-soluble, co-precipitation, water washing and precipitating, calcium content greatly reduces, and the change of other tenors is relatively little.According to the Precipitation of calcium ion, in catalyst, calcium content is relevant with the pH of precipitation and washing, and high pH is conducive to calcium ions precipitate and is formed.When washing close to time neutral, calcium ion is washed out substantially in filtrate.Therefore, prepare the catalyst that calcium content is high, can suitably improve precipitation pH value, and control the consumption of washings.Characterize through nitrogen adsorption and find, slag raw material ratio surface area is very little, only has 2.9m
2/ g.Compared to slag raw material, after different sintering temperature activation, specific surface area of catalyst is greatly enhanced, and after different temperatures calcining, specific area is all higher than 150m
2/ g, especially after low temperature 350 DEG C of roastings, specific surface area of catalyst is up to 298m
2/ g.The Adsorption and desorption isotherms of catalyst nitrogen is shown in Fig. 1.
Embodiment 2
Take 3.0g urethanes, 15.5g ethanol and 0.15g SN-350 catalyst, add 100mL stainless steel cauldron, closed reactor.Under magnetic agitation, temperature controller control temperature rises to 200 DEG C, and react 3 hours, be cooled to room temperature, gas reactor slowly discharges reactor by pressure-control valve.Treat that gas reactor release is complete, drive still and collect reaction mixture.Get a certain amount of product, after volumetric flask constant volume, adopt Shimadzu chromatographic, wherein chromatograph configuration flame ionization ditector (FID) and polarity capillary column (Rtx-530m × 0.25mm × 0.25 μm).Analysis result shows, urethane ester conversion rate 51.4%, diethyl carbonate yield 37.4%.
Embodiment 3
Adopt as embodiment 2 same reaction step, only changing catalyst is SN-450, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 44.5%, diethyl carbonate yield 33.1%.
Embodiment 4
Adopt as embodiment 2 same reaction step, only changing catalyst is SN-550, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 24.8%, diethyl carbonate yield 17.2%.
Embodiment 5
Adopt as embodiment 2 same reaction step, only changing catalyst is SN-650, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 48.4%, diethyl carbonate yield 7.6%.
Embodiment 6
Adopt step as similar in embodiment 1, only change precipitating reagent ammoniacal liquor, Kaolinite Preparation of Catalyst is labeled as SN-A-450, adopts as embodiment 2 same reaction step, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 51.8%, diethyl carbonate yield 23.1%.
Embodiment 7
Adopt embodiment 1 Kaolinite Preparation of Catalyst, changing catalyst pH is 11.5, be labeled as SN-11.5-450, synthesizing diethyl carbonate adopts as embodiment 3 same reaction step, only changing catalyst is SN-11.5-450, reaction terminates rear sampling and analyzes, urethane ester conversion rate 39.5%, diethyl carbonate yield 25.1%.
Embodiment 8
Adopt as embodiment 3 same reaction step, only changing catalyst amount is 0.05g, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 25.0%, diethyl carbonate yield 16.8%.
Embodiment 9
Adopt as embodiment 3 same reaction step, only changing catalyst amount is 0.10g, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 38.3%, diethyl carbonate yield 27.6%.
Embodiment 10
Adopt as embodiment 3 same reaction step, only changing reaction temperature is 190 DEG C, and reaction terminates rear sampling and analyzes, and urethane ester conversion rate 14.8%, diethyl carbonate yield 8.3%, shows that cryogenic conditions is unfavorable for the generation of diethyl carbonate.
Embodiment 11
Adopt as embodiment 3 same reaction step, only changing reaction temperature is 210 DEG C, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 54.9%, diethyl carbonate yield 43.6%.
Embodiment 12
Adopt as embodiment 3 same reaction step, only changing EC consumption is 2.0g, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 46.0%, diethyl carbonate yield 28.5%.
Embodiment 13
Adopt as embodiment 3 same reaction step, only changing EC consumption is 4.5g, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 51.9%, diethyl carbonate yield 40.0%.
Embodiment 14
Adopt as embodiment 3 same reaction step, only changing the reaction time is 2h, and reaction terminates rear sampling and analyzes, urethane ester conversion rate 39.3%, diethyl carbonate yield 30.4%.
Embodiment 15
Catalyst is reused experiment and is carried out as follows, and catalyst, after centrifugation, removes supernatant liquor, through ethanol purge, after baking oven heat drying or 450 degree of roastings, as reusable catalyst.Take 3.0g urethanes, 15.5g ethanol and the catalyst reusing 5 times, course of reaction is as embodiment 3, and after reaction terminates, chromatography is carried out in sampling.After repeatedly using, result as shown in Figure 5, and result shows, catalyst, after repeatedly using, still maintains more than 27% DEC yield.
Comparative example 1
Take the former powder of 0.15g slag, 3.0g urethanes and 15.5g ethanol, course of reaction is see embodiment 2, analysis result shows, urethane ester conversion rate 9.0%, diethyl carbonate yield 6.0%, shows directly to use slag lower as catalyst activity, and urethane ester conversion rate and diethyl carbonate yield are starkly lower than the catalyst that embodiment 2-3 is prepared through post processing.
Comparative example 2
30g FeCl
3h
2o is dissolved in 300mL deionized water, in continuous whipping process, dropwise adds 2mol/L NaOH solution, control pH scope 4-5, and gained is deposited in 80-100 DEG C of ageing, after filtration, washing, after drying, in 450 DEG C of roasting 3h, obtains Fe
2o
3catalyst.
Adopt above-mentioned preparation process, with Al
2(SO
4)
318H
2o is aluminium source, control pH scope 7-8, preparation Al
2o
3catalyst; Same, adopt MgCl
2for magnesium source, preparation MgO catalyst.
Take the above-mentioned catalyst of 0.15g respectively, 3.0g urethanes and 15.5g ethanol, course of reaction is see embodiment 2, and analysis result is as shown in the table:
| Catalyst | EC Con./% | DEC Yield/% |
| MgO | 26.7 | 21.3 |
| Al 2O 3 | 13.7 | 2.2 |
| Fe 2O 3 | 21.8 | 4.5 |
Compared with slag Kaolinite Preparation of Catalyst, one-component catalyst activity is starkly lower than slag based solid alkali catalyst.The above results shows effectively to utilize prepared from steel slag for high-activity solid base catalyst, and the catalytic activity with excellence prepared in diethyl carbonate process by this catalyst at urethanes and ethanol synthesis.
In a word, the present invention utilizes slag solid waste, and prepare poly-metal deoxide solid base catalyst, preparation process is simple and practical, and effectively can reduce the cost of catalyst, type solid base has extremely wide application prospect as an alternative.This catalyst has excellent catalytic activity to synthesis high added value fine chemicals diethyl carbonate simultaneously, and has environmental friendliness, the advantage such as corrosion-free, pollution-free, is easy to realize commercial Application.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claims of the present invention and appurtenance completely, implementation procedure and the same the various embodiments described above of method; And non-elaborated part of the present invention belongs to techniques well known.
The above, be only some embodiments of the present invention, but the present invention is not limited to above-mentioned method detailed.The personnel of art, in the technical scope that the present invention discloses, to any improvement that the present invention is carried out the present invention by modes such as equivalence replacement or interpolation auxiliary elements, should be encompassed within protection scope of the present invention.
Claims (12)
1. slag metal oxides solid base catalyst preparation method, it is characterized in that the raw material sources of catalyst are in trade waste slag, preparation process comprises the steps:
(1) slag powder is dissolved as corresponding metal salt solution under agitation in certain density inorganic acid solution, described inorganic acid solution concentration range is 1mol/L to 12mol/L, and the mass percent scope slag/hydrochloric acid solution of slag and inorganic acid solution is 1:5 to 1:50;
(2) stirring condition is be warming up to 80-120 DEG C under stir speed (S.S.) 100-500rpm, and heating makes the silicon species in slag be polymerized, and crosses and filters polymerization silicon species, obtain metalline filtrate;
(3) gained metalline filtrate is titrated to pH=8-13 through alkaline precipitating agent, generates solid sediment, and in 20-120 DEG C of ageing;
(4) gained sediment after filtration, washing, dry, obtain roasting procatalyst presoma;
(5) gained catalyst precursor is through calcination activation, sintering temperature 200 DEG C-1200 DEG C, obtain poly-metal deoxide solid base catalyst, its composition is relevant with the composition of slag raw material used, comprise containing magnesium, iron, aluminium, calcium, chlorine, account for more than catalyst gross mass 90wt% with the form of oxide and chlorine with normalization method calculating, surplus is the micro constitutent comprising manganese, titanium.
2. slag metal oxides solid base catalyst preparation method as claimed in claim 1, is characterized in that: the slag in described step (1) is selected from one or more mixtures in vessel slag, open hearth slag, electroslag.
3. slag metal oxides solid base catalyst preparation method as claimed in claim 1, is characterized in that: described step (1) slag powder selects particle diameter to be less than the particle of 3mm.
4. slag metal oxides solid base catalyst preparation method as claimed in claim 1, it is characterized in that: the inorganic acid in described step (1) is selected from one or more mixtures in hydrochloric acid, sulfuric acid, nitric acid, concentration range is 0.1-10mol/L.
5. slag metal oxides solid base catalyst preparation method as claimed in claim 1, it is characterized in that: the alkaline precipitating agent in described step (3) is selected from one or more mixtures in sodium carbonate, potash, NaOH, potassium hydroxide, ammoniacal liquor, urea, potassium phosphate, sodium phosphate, its concentration is 0.5-12mol/L.
6. slag metal oxides solid base catalyst preparation method as claimed in claim 1, is characterized in that: in described step (5), catalyst precursor is selected from the one of air, nitrogen, argon gas, vacuum through the gas that roasting is; One in preferred air, nitrogen.
7. slag metal oxides solid base catalyst preparation method as claimed in claim 1, is characterized in that: the sintering temperature in described step (5) 300 DEG C-900 DEG C; Preferably 300 DEG C-600 DEG C further.
8. the method for slag metal oxides catalyst synthesizing diethyl carbonate, it is characterized in that: under the catalytic action of the catalyst prepared in claim 1, urea or urethanes and ethanol generation alcoholysis reaction is made to prepare diethyl carbonate, simultaneously ammonia gas as byproduct; The molar ratio range of described ethanol and urea or urethanes is ethanol/urea or urethanes=2-20; Described catalyst amount is the 0.01wt%-5wt% based on reactant liquor gross mass; Described reaction temperature 160-220 DEG C; Reaction time is 0.1h-5h.
9., as claim requires synthesizing diethyl carbonate method as described in 8, it is characterized in that: the molar ratio range of described ethanol and urea or urethanes is ethanol/urea or urethanes=4-12.
10., as claim requires synthesizing diethyl carbonate method as described in 8, it is characterized in that: described catalyst amount is the 0.05wt%-2wt% based on reactant liquor gross mass.
11. require synthesizing diethyl carbonate method as described in 8 as claim, it is characterized in that: described reaction temperature is 180 DEG C-210 DEG C.
12. require synthesizing diethyl carbonate method as described in 8 as claim, it is characterized in that: the described reaction time is 1h-3h.
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| CN105671225A (en) * | 2016-01-22 | 2016-06-15 | 山东钢铁股份有限公司 | Method for comprehensively using blast furnace slag and converter slag |
| CN106953102A (en) * | 2017-05-18 | 2017-07-14 | 山西大学 | It is a kind of for catalyst of carbon consuming cell and preparation method thereof |
| CN109939706A (en) * | 2017-12-20 | 2019-06-28 | 财团法人工业技术研究院 | The manufacturing method of catalyst and its manufacturing method and artificial fuel gas |
| CN115057777A (en) * | 2022-07-14 | 2022-09-16 | 山东德普新材料科技有限公司 | Method for directly preparing dimethyl carbonate by adopting urea alcoholysis method and application thereof |
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Application publication date: 20150715 |