CN102000569A - Catalyst for producing furan by furfural liquid-phase decarbonylation and preparation method - Google Patents
Catalyst for producing furan by furfural liquid-phase decarbonylation and preparation method Download PDFInfo
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Abstract
The invention provides a catalyst for producing furan by furfural liquid-phase decarbonylation and a preparation method. In the catalyst, expression gamma-Al2O3 and MO are taken as a composite carrier and the promoter MO is oxides of K, Cs or Li. MO accounts for 0.5-2.0wt% of the composite carrier. The active component of the catalyst is Pd and the parent of Pd is PdCl2 (or Pd(NO3)2 or [Pd(C2H3O2)2]3. Pd accounts for 5wt% of the composite carrier. The catalyst is prepared by means of dipping precipitation and has good activity in furfural liquid-phase decarbonylation reaction with furfural percent conversion of 92.5-98.2%, furan selectivity of 85.3-94.2% and has long service life of 100-120h.
Description
Technical field
The present invention relates to a kind of furfural liquid phase decarbonylation and produce the catalyst and the method for making thereof of furans.
Background technology
Furfural is important Organic Chemicals, and China produces furfural per year and reaches tens0000 tons, but most of as cheap chemical industry material outlet, in order to improve the economic benefit of furfural manufacturing enterprise, must develop the high attached value spin-off of furfural energetically.Furans is a kind of important medicine and agricultural chemicals organic intermediate, is widely used in many important organic syntheses and medicine production, and it can also be used to producing pyrroles, thiophene, oxolane (THF) etc.And oxolane (THF) is important solvent, can also be used to make polyurethane fiber, polyurethane elastomer.Therefore, exploitation decarbonylation of furfural system furans and oxolane (THF) process have important practical application meaning.
The production of furans mainly contains two lines, article one, be to produce by butadiene or crotonaldehyde catalytic oxidation, article one, be to produce by furfural catalysis decarbonylation, the former is restricted its commercial Application because the selectivity of reaction-ure conversion-age and furans is low, the decarbonylation selectivity and the furans productive rate of furfural method are higher, thereby research is comparatively extensive, has become to take as the leading factor production method.The catalyst system of producing furans is more, early oxidation decarbonylation catalyst such as soda lime, PbO and HgO are arranged, but since problems such as active low and catalyst toxicity be eliminated.The oxidation decarbonylation catalyst in 60-70 age in 20th century has Zn-Cr, Zn-Fe-Mn, and Zn-Cr-Fe, metal oxide catalysts such as Zn-Cd-Mn-Al, but because stability is not good enough, catalyst life is short, production capacity is little, severe reaction conditions and being abandoned gradually.The research of decarbonylation of furfural system furans catalyst is mainly laid particular emphasis on noble metal catalyst from the later stage seventies 20th century, as palladium system, platinum group and rhodium series catalysts, palladium are to study maximum catalyst so far.
Produce in the furans process at present furfural liquid phase decarbonylation, employed catalyst mainly is Pd/C, Pd/ nanometer γ-Al
2O
3Catalyst.
Jung discovers, when using the 5%Pd/C catalyst to carry out the liquid phase decarbonylation, be reflected at 159～162 ℃ carry out 100h after, catalyst activity reduces to 62.5%, average every gram palladium is produced furans 36kg;
People such as Shi Jun discover, when using the 2%Pd/C catalyst to carry out the liquid phase decarbonylation, be reflected at carry out a period of time under 180～200 ℃ after, the yield of furans reaches 91.06%.
Introduced a kind of furfural liquid phase decarbonylation system furans Preparation of catalysts method in the patent 200810050517.6, adopt this kind catalyst, be reflected under 200～250 ℃ and carry out, the furans yield reaches 90.25%～95%, but in preparation process, exist filtration difficulty, the problem that the palladium loss amount is big.Therefore in amplification process, be restricted.
In recent years, the development of the furfurol industry of China is swift and violent, and the space, domestic market is limited, and drug on the market to cause furfural, and intense market competition causes the furfural domestic price on the low side all the time, and the result causes 70% above product to export at a low price.Yet supply falls short of demand again for furfural deep processed products such as Chinese domestic furans, oxolane, and this has just caused and has exported furfural at a low price, but asks an exorbitant fare from the situation of products such as external import oxolane.Thereby, greatly develop furfural → furans → furfural deep processing industries such as oxolane and be more suitable for national conditions, have bigger economic implications.In addition, along with the reinforcement of countries in the world environmental consciousness, when this process of development decarbonylation of furfural system furans, also need to consider its influence to environment, exploitation effective catalyst and environmentally friendly technology will have huge realistic meaning.
Summary of the invention
The object of the invention provides catalyst and the method for making thereof that a kind of furfural liquid phase decarbonylation is produced furans.It is the Catalysts and its preparation method of the furfural liquid phase decarbonylation production furans of a kind of high activity, high selectivity, life-span length, good stability.
A kind of furfural liquid phase decarbonylation of the present invention is produced the catalyst of furans, and the complex carrier of this catalyst is γ-Al
2O
3With the composition of MO, wherein, MO is the oxide of K, Cs or Li, and MO accounts for 0.5～2.0wt% of described complex carrier;
The oxide of K, Cs or Li is a co-catalyst in the complex carrier of described catalyst;
Described activity of such catalysts component is Pd, and the parent of described active component Pd is PdCl
2(or Pd (NO
3)
2Or [Pd (C
2H
3O
2)
2]
3, wherein, Pd accounts for the 5wt% of described complex carrier.
A kind of furfural liquid phase decarbonylation of the present invention is produced the catalyst of furans, adopts the preparation of dipper precipitation method, and its step and condition are as follows
(a) γ-Al
2O
3Preparation with the MO complex carrier
Account for the proportioning of 0.5～2.0wt% of described complex carrier according to MO, with γ-Al
2O
3In the aqueous solution of K, Cs that immerses or the salt of Li, make γ-Al
2O
3Just soaked into fully by the aqueous solution of K, Cs or Li salt, under mechanical agitation, flood 4h down in 60 ℃, in 100～120 ℃ of down dry 4～8h, 450～600 ℃ of roasting 3～6h grind gains then and sieve, obtain the complex carrier of catalyst, described MO is the oxide of K, Cs or Li, and the granularity of described complex carrier is 200 orders, and the saline solution of described K, Cs or Li is hydrochloride, nitrate or the acetate aqueous solution of K, Cs or Li;
(b) a kind of Preparation of catalysts of furfural liquid phase decarbonylation production furans accounts for the 5wt% of described complex carrier according to Pd; in three mouthfuls of containers; the salting liquid that adds Pd; logical nitrogen deoxygenation; logical nitrogen protection and heating are injected into precipitating reagent in three mouthfuls of containers with dropping funel under mechanical agitation, after adjusting the pH value for the first time and being 0.5≤pH≤5; stop to add precipitating reagent, according to the proportioning impregnation steps
(a) Zhi Bei complex carrier, dipping temperature is 20～60 ℃, dip time is 1h, add for the second time after precipitating reagent adjusts the pH value and be 5＜pH≤9, stop to add precipitating reagent, continue dipping, dip time is 4～24h, and dipping temperature is 20～60 ℃, add once more for the third time after precipitating reagent adjusts the pH value and be 9＜pH≤12, add reducing agent, the consumption of reducing agent is 10 times of theoretical value, and described theoretical value can be respectively calculated by the reaction equation of palladium salt and reducing agent, reduction temperature is 20～60 ℃, recovery time is 2～4h, in 80～100 ℃ of vacuum drying 3～8h, makes the target catalyst behind the suction filtration;
The salting liquid of described Pd is PdCl
2, Pd (NO
3)
2Or [Pd (C
2H
3O
2)
2]
3Solution;
Described precipitating reagent is a sodium carbonate, sodium acid carbonate, NaOH, ammonium carbonate, one or more of urea;
Described reducing agent is one or more of methyl alcohol, ethanol, formaldehyde, sodium borohydride, hydrazine hydrate or glucose.
A kind of furfural liquid phase decarbonylation is produced the usage of the catalyst of furans, the condition that described catalyst is used for furfural liquid phase decarbonylation production furans is as follows: pressure 0～0.5MPa, 200～250 ℃ of temperature, react 3～10h under the condition of mixing speed 100～200r/min, the catalyst addition is furfural 0.5%～2wt%.
Beneficial effect: this kind catalyst has good activity in furfural liquid phase decarbonylation reaction, furfural conversion ratio 92.5%-98.2%, and furans selectivity 85.3%-94.2%, catalyst life is long, reaches 100-120h.
The specific embodiment
Embodiment 1
(a) γ-Al
2O
3And K
2The preparation of O complex carrier
According to K
2O accounts for the proportioning of the 0.5wt% of described complex carrier, with γ-Al of 5g
2O
3Be immersed in 0.054gKNO
3The aqueous solution in, make γ-Al
2O
3Just by KNO
3The aqueous solution soak into fully, under mechanical agitation, in 60 ℃ of following dipping 4h, in 100 ℃ of dry 4h down, 450 ℃ of roasting 3h ground gains 200 mesh sieve then, obtained the complex carrier of powder catalyst.
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to palladium (Pd), with the PdCl of 0.5g
2Be dissolved in the hydrochloric acid solution of 50mL, concentration of hydrochloric acid is 0.1mol/L, treat that it dissolves fully after, it is poured in the there-necked flask of 250mL into logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation.With 5g NaHCO
3Be dissolved in the 50mL distilled water, it slowly be injected in the there-necked flask, adjust solution PH to 05, stop to add NaHCO with dropping funel
3Solution, the γ-Al that will make above then
2O
3/ K
2The O complex carrier is poured in the there-necked flask, floods 1h down at 20 ℃, uses NaHCO
3Solution stops to add NaHCO after adjusting PH to 5
3Solution continues dipping 4h, and dipping temperature is 20 ℃, adds NaHCO once more
3Solution stops to add NaHCO after adjusting PH to 9
3Solution is the mass fraction of 2.12g that 40% formalin evenly is added drop-wise to reductase 12 h in the system with dropping funel then, and reduction temperature is 20 ℃, at 80 ℃ of following vacuum drying 3h, makes the target catalyst then.
For the reducing agent theoretical value, in this explanation for example, be reducing agent with formaldehyde, then reaction equation is:
HCHO+H
2O+pd
2+＝Pd+HCOOH+2H
+
In this embodiment, the palladium bichloride consumption is 0.5g, and the corresponding theoretical value of calculating the formaldehyde consumption is 0.085g, and then actual amount is 0.85g, and the corresponding mass mark is that 40% formalin then is 2.12g.
Also be based on same reason for other reducing agent and calculate, described theoretical value can be respectively calculated by the reaction equation of palladium salt and reducing agent.
The above-mentioned catalyst of 1.0g is put into reactor, pour the 100g furfural then into, carry out furfural liquid phase decarbonylation reaction 4h under the condition of pressure 0～0.5MPa, 230 ℃ of temperature, mixing speed 100～200r/min, the furfural conversion ratio is 95.5%, and selectivity is 85.2%.
Embodiment 2～11
(a) γ-Al
2O
3With the condition such as the table 1 of the preparation of MO complex carrier, all the other conditions are with embodiment 1.
Table 1
Annotate: in the table 1, mass fraction wt% be MO account for described complex carrier the proportioning value.
(b) a kind of furfural liquid phase decarbonylation is produced Preparation of catalysts condition such as the table 2 and the table 3 of furans, and all the other conditions are with embodiment 1.
Table 2
Table 3
| Embodiment | Palladium salt | Precipitating reagent | Reducing agent |
| 2 | Palladium nitrate | Sodium carbonate | Methyl alcohol |
| 3 | Palladium | NaOH | Ethanol |
| 4 | Palladium bichloride | Ammonium carbonate | Sodium borohydride |
| 5 | Palladium nitrate | Urea | Hydrazine hydrate |
| 6 | Palladium | Sodium acid carbonate | Glucose |
| 7 | Palladium nitrate | NaOH | Formaldehyde |
| 8 | Palladium | Urea | Hydrazine hydrate |
| 9 | Palladium bichloride | Sodium carbonate | Ethanol |
| 10 | Palladium bichloride | Sodium acid carbonate | Hydrazine hydrate |
The catalytic effect of the catalyst that embodiment 2-10 obtains sees Table 4, and the condition of concrete catalysis usage is with the catalytic condition of catalyst among the embodiment 1.
Table 4
| Embodiment | The furfural conversion ratio | The furans selectivity |
| Embodiment 2 | 95.5％ | 88.2％ |
| Embodiment 3 | 92.5％ | 86.3％ |
| Embodiment 4 | 93.0％ | 87.0％ |
| Embodiment 5 | 93.1％ | 86.2％ |
| Embodiment 6 | 94.8％ | 89.3％ |
| Embodiment 7 | 95.2％ | 91.2％ |
| Embodiment 8 | 95.1％ | 90.4％ |
| Embodiment 9 | 95.0％ | 85.3％ |
| Embodiment 10 | 98.2％ | 94.2％ |
Claims (13)
1. a furfural liquid phase decarbonylation is produced the furans catalyst, it is characterized in that the complex carrier of this catalyst is γ-Al
2O
3With the composition of MO, wherein, MO is the oxide of K, Cs or Li, and MO accounts for 0.5～2.0wt% of described complex carrier;
The oxide of K, Cs or Li is a co-catalyst in the complex carrier of described catalyst;
Described activity of such catalysts component is Pd, and the parent of described active component Pd is PdCl
2(or Pd (NO
3)
2Or [Pd (C
2H
3O
2)
2]
3, wherein, Pd accounts for the 5wt% of described complex carrier.
2. a kind of furfural liquid phase decarbonylation according to claim 1 is produced the furans catalyst, it is characterized in that the granularity of described complex carrier is 200 orders.
3. a kind of furfural liquid phase decarbonylation according to claim 1 is produced the method for making of furans with catalyst, it is characterized in that step and condition are as follows:
(a) γ-Al
2O
3Preparation with the MO complex carrier
Account for the proportioning of 0.5～2.0wt% of described complex carrier according to MO, with γ-Al
2O
3In the aqueous solution of K, Cs that immerses or the salt of Li, make γ-Al
2O
3Just soaked into fully by the aqueous solution of K, Cs or Li salt, under mechanical agitation, flood 4h down in 60 ℃, in 100～120 ℃ of down dry 4～8h, 450～600 ℃ of roasting 3～6h grind gains then and sieve, obtain the complex carrier of catalyst, described MO is the oxide of K, Cs or Li, and the granularity of described complex carrier is 200 orders, and the saline solution of described K, Cs or Li is hydrochloride, nitrate or the acetate aqueous solution of K, Cs or Li;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, in three mouthfuls of containers, the salting liquid that adds Pd, logical nitrogen deoxygenation, logical nitrogen protection and heating under mechanical agitation, with dropping funel precipitating reagent is injected in three mouthfuls of containers, after for the first time adjusting the pH value and being 0.5≤pH≤5, stops to add precipitating reagent, complex carrier according to proportioning impregnation steps (a) preparation, dipping temperature is 20～60 ℃, and dip time is 1h, adds for the second time after precipitating reagent adjusts the pH value and be 5＜pH≤9, stop to add precipitating reagent, continue dipping, dip time is 4～24h, and dipping temperature is 20～60 ℃, add once more for the third time after precipitating reagent adjusts the pH value and be 9＜pH≤12, add reducing agent, the consumption of reducing agent is 10 times of theoretical value, and described theoretical value can be respectively calculated by the reaction equation of palladium salt and reducing agent, reduction temperature is 20～60 ℃, recovery time is 2～4h, in 80～100 ℃ of vacuum drying 3～8h, makes the target catalyst behind the suction filtration;
The salting liquid of described Pd is PdCl
2, Pd (NO
3)
2Or [Pd (C
2H
3O
2)
2]
3Solution;
Described precipitating reagent is a sodium carbonate, sodium acid carbonate, NaOH, ammonium carbonate, one or more of urea;
Described reducing agent is one or more of methyl alcohol, ethanol, formaldehyde, sodium borohydride, hydrazine hydrate or glucose.
4. a kind of furfural liquid phase decarbonylation according to claim 3 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3And K
2The preparation of O complex carrier
According to K
2O accounts for the proportioning of the 0.5wt% of described complex carrier, with γ-Al
2O
3Be immersed in KNO
3The aqueous solution in, make γ-Al
2O
3Just by KNO
3The aqueous solution soak into fully, under mechanical agitation, in 60 ℃ of following dipping 4h, in 100 ℃ of dry 4h down, 450 ℃ of roasting 3h ground gains 200 mesh sieve then, obtained the complex carrier of powder catalyst.
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, with PdCl
2Hydrochloric acid solution pour in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation are with NaHCO
3The aqueous solution is injected in the there-necked flask with dropping funel, adjusts pH value of solution value to 0.5, stops to add NaHCO
3Solution, the γ-Al that will make above then
2O
3And K
2The O complex carrier is poured in the there-necked flask, floods 1h down at 20 ℃, uses NaHCO
3Solution stops to add NaHCO after adjusting pH value to 5
3Solution continues dipping 4h, and dipping temperature is 20 ℃, adds NaHCO once more
3Solution stops to add NaHCO after adjusting pH value to 9
3Solution evenly is added drop-wise to reductase 12 h in the system to reducing agent formalin with dropping funel then, and the consumption of reducing agent is 10 times of theoretical value, and reduction temperature is 20 ℃, at 80 ℃ of following vacuum drying 3h, makes the target catalyst then; Described theoretical value is calculated by the reaction equation of palladium salt and reducing agent formaldehyde.
5. a kind of furfural liquid phase decarbonylation according to claim 4 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3And K
2The preparation of O complex carrier
According to K
2O accounts for the proportioning of the 0.5wt% of described complex carrier, with γ-Al
2O
3Be immersed in the aqueous solution of potassium acetate dry 4.5h under 100 ℃, 450 ℃ of roasting 3.5h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium nitrate solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With sodium carbonate liquor, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 1 for the first time, stop to add sodium carbonate liquor, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 20 ℃, after adjusting pH value to 5.5 for the second time with sodium carbonate liquor, stop to add sodium carbonate liquor, continue dipping 6h for the second time, dipping temperature is 20 ℃ for the second time, after adding sodium carbonate liquor adjustment pH value to 9.5 for the third time, stop to add sodium carbonate liquor, then the reducing agent methanol solution evenly is added drop-wise to reductase 12 h in the system with dropping funel, the consumption of reducing agent is 10 times of theoretical value, and reduction temperature is 20 ℃, at 85 ℃ of following vacuum drying 3.5h, make the target catalyst then; The theoretical value of described reducing agent methyl alcohol is calculated by the reaction equation of palladium nitrate salt and reducing agent methyl alcohol;
Remaining condition is with claim 4.
6. a kind of furfural liquid phase decarbonylation according to claim 3 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3Preparation with the cesium oxide complex carrier
Account for the proportioning of the 0.7wt% of described complex carrier according to cesium oxide, with γ-Al
2O
3Be immersed in the aqueous solution of cesium nitrate dry 5h under 105 ℃, 500 ℃ of roasting 4h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With sodium hydroxide solution, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 1.5 for the first time, stop to add sodium carbonate liquor, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 25 ℃, after adjusting pH value to 6 for the second time with sodium hydroxide solution, stop to add sodium hydroxide solution, continue dipping 9h for the second time, dipping temperature is 25 ℃ for the second time, after adding sodium hydroxide solution adjustment pH value to 10 for the third time, stop to add sodium hydroxide solution, then the reducing agent ethanolic solution evenly is added drop-wise to reductase 12 .5h in the system with dropping funel, the reducing agent consumption of ethanol is 10 times of theoretical value, and reduction temperature is 25 ℃, at 90 ℃ of following vacuum drying 4h, make the target catalyst then; The theoretical value of described reducing agent ethanol is calculated by the reaction equation of palladium salt and reducing agent ethanol;
Remaining condition is with claim 4.
7. a kind of furfural liquid phase decarbonylation according to claim 4 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3Preparation with the lithia complex carrier
Account for the proportioning of the 0.9wt% of described complex carrier according to lithia, with γ-Al
2O
3Be immersed in the aqueous solution of lithium chloride dry 5.5h under 110 ℃, 550 ℃ of roasting 4.5h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium chloride solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With sal volatile, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 2 for the first time, stop to add sal volatile, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 30 ℃, after adjusting pH value to 6.5 for the second time with sal volatile, stop to add sal volatile, continue dipping 12h for the second time, dipping temperature is 30 ℃ for the second time, after adding sal volatile adjustment pH value to 10.5 for the third time, stop to add sal volatile, then the borane reducing agent sodium hydride solution evenly is added drop-wise to dropping funel and reduces 3h in the system, the consumption of borane reducing agent sodium hydride is 10 times of theoretical value, and reduction temperature is 30 ℃, at 95 ℃ of following vacuum drying 4.5h, make the target catalyst then; The theoretical value of described borane reducing agent sodium hydride is calculated by the reaction equation of palladium bichloride salt and borane reducing agent sodium hydride;
Remaining condition is with claim 4.
8. a kind of furfural liquid phase decarbonylation according to claim 4 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3Preparation with the potassium oxide complex carrier
Account for the proportioning of the 1.1wt% of described complex carrier according to potassium oxide, with γ-Al
2O
3Be immersed in the aqueous solution of potassium chloride dry 6h under 115 ℃, 600 ℃ of roasting 5h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium nitrate solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With urea liquid, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 2.5 for the first time, stop to add urea liquid, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 35 ℃, after adjusting pH value to 7 for the second time with urea liquid, stop to add urea liquid, continue dipping 15h for the second time, dipping temperature is 35 ℃ for the second time, after adding urea liquid adjustment pH value to 11 for the third time, stop to add urea liquid, then the reducing agent hydrazine hydrate solution evenly is added drop-wise to dropping funel and reduces 3.5h in the system, the consumption of reducing agent hydrazine hydrate is 10 times of theoretical value, and reduction temperature is 35 ℃, at 100 ℃ of following vacuum drying 5h, make the target catalyst then; The theoretical value of described reducing agent hydrazine hydrate is calculated by the reaction equation of palladium nitrate salt and reducing agent hydrazine hydrate;
Remaining condition is with claim 4.
9. a kind of furfural liquid phase decarbonylation according to claim 4 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3Preparation with the cesium oxide complex carrier
Account for the proportioning of the 1.3wt% of described complex carrier according to cesium oxide, with γ-Al
2O
3Be immersed in the aqueous solution of cesium chloride dry 6.5h under 120 ℃, 600 ℃ of roasting 5.5h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With sodium bicarbonate solution, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 3 for the first time, stop to add sodium bicarbonate solution, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 40 ℃, after adjusting pH value to 7.5 for the second time with sodium bicarbonate solution, stop to add sodium bicarbonate solution, continue dipping 18h for the second time, dipping temperature is 40 ℃ for the second time, after adding urea liquid adjustment pH value to 11.5 for the third time, stop to add sodium bicarbonate solution, then the reducing agent glucose solution evenly is added drop-wise to dropping funel and reduces 4h in the system, the consumption of reducing agent glucose is 10 times of theoretical value, and reduction temperature is 40 ℃, at 100 ℃ of following vacuum drying 5.5h, make the target catalyst then; The theoretical value of described reducing agent glucose is calculated by the reaction equation of palladium nitrate salt and reducing agent glucose;
Remaining condition is with claim 4.
10. a kind of furfural liquid phase decarbonylation according to claim 4 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3Preparation with the cesium oxide complex carrier
Account for the proportioning of the 1.5wt% of described complex carrier according to cesium oxide, with γ-Al
2O
3Be immersed in the aqueous solution of cesium acetate dry 7h under 120 ℃, 600 ℃ of roasting 6h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium nitrate solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With sodium hydroxide solution, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 3.5 for the first time, stop to add sodium hydroxide solution, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 45 ℃, after adjusting pH value to 8 for the second time with sodium hydroxide solution, stop to add sodium hydroxide solution, continue dipping 21h for the second time, dipping temperature is 45 ℃ for the second time, after adding sodium hydroxide solution adjustment pH value to 12 for the third time, stop to add sodium hydroxide solution, then reducing agent formalin evenly is added drop-wise to dropping funel and reduces 4h in the system, the consumption of reducing agent formaldehyde is 10 times of theoretical value, and reduction temperature is 45 ℃, at 100 ℃ of following vacuum drying 6h, make the target catalyst then; The theoretical value of described reducing agent formaldehyde is calculated by the reaction equation of palladium nitrate salt and reducing agent formaldehyde;
11. a kind of furfural liquid phase decarbonylation according to claim 4 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3Preparation with the lithia complex carrier
Account for the proportioning of the 1.7wt% of described complex carrier according to lithia, with γ-Al
2O
3Be immersed in the aqueous solution of lithium acetate dry 7.5h under 120 ℃, 600 ℃ of roasting 6h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With urea liquid, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 4 for the first time, stop to add urea liquid, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 50 ℃, after adjusting pH value to 8.5 for the second time with urea liquid, stop to add urea liquid, continue dipping 24h for the second time, dipping temperature is 50 ℃ for the second time, after adding urea liquid adjustment pH value to 12 for the third time, stop to add urea liquid, then the reducing agent hydrazine hydrate solution evenly is added drop-wise to dropping funel and reduces 4h in the system, the consumption of reducing agent hydrazine hydrate is 10 times of theoretical value, and reduction temperature is 50 ℃, at 100 ℃ of following vacuum drying 6.5h, make the target catalyst then; The theoretical value of described reducing agent hydrazine hydrate is calculated by the reaction equation of palladium salt and reducing agent hydrazine hydrate;
Remaining condition is with claim 4.
12. a kind of furfural liquid phase decarbonylation according to claim 4 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3Preparation with the lithia complex carrier
Account for the proportioning of the 2.0wt% of described complex carrier according to lithia, with γ-Al
2O
3Be immersed in the aqueous solution of lithium nitrate dry 8h under 120 ℃, 600 ℃ of roasting 6h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium chloride solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With sodium carbonate liquor, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 5 for the first time, stop to add sodium carbonate liquor, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 60 ℃, after adjusting pH value to 9 for the second time with sodium carbonate liquor, stop to add sodium carbonate liquor, continue dipping 24h for the second time, dipping temperature is 60 ℃ for the second time, after adding sodium carbonate liquor adjustment pH value to 12 for the third time, stop to add sodium carbonate liquor, then the reducing agent ethanolic solution evenly is added drop-wise to dropping funel and reduces 4h in the system, the reducing agent consumption of ethanol is 10 times of theoretical value, and reduction temperature is 60 ℃, vacuum drying 8h under 100C makes the target catalyst then; The theoretical value of described reducing agent ethanol is calculated by the reaction equation of palladium bichloride salt and reducing agent ethanol;
Remaining condition is with claim 4.
13. a kind of furfural liquid phase decarbonylation according to claim 4 is produced the method for making of furans with catalyst, it is characterized in that, and is described:
(a) γ-Al
2O
3Preparation with the potassium oxide complex carrier
Account for the proportioning of the 2.0wt% of described complex carrier according to potassium oxide, with γ-Al
2O
3Be immersed in the aqueous solution of potassium nitrate dry 8h under 120 ℃, 500 ℃ of roasting 6h;
(b) a kind of furfural liquid phase decarbonylation is produced the Preparation of catalysts of furans
Account for the 5wt% of described complex carrier according to Pd, palladium chloride solution is poured in the there-necked flask, logical nitrogen 10min deoxygenation, logical nitrogen protection and heating under mechanical agitation; With sodium bicarbonate solution, be injected in the there-necked flask with dropping funel, adjust pH value of solution value to 1 for the first time, stop to add sodium bicarbonate solution, then γ-the Al that will make above
2O
3/ K
2The O complex carrier is poured in the there-necked flask, flood for the first time 1h down at 45 ℃, after adjusting pH value to 8 for the second time with sodium bicarbonate solution, stop to add sodium bicarbonate solution, continue dipping 4h for the second time, dipping temperature is 60 ℃ for the second time, after adding sodium bicarbonate solution adjustment pH value to 9 for the third time, stop to add sodium bicarbonate solution, then the reducing agent hydrazine hydrate solution evenly is added drop-wise to reductase 12 h in the system with dropping funel, the consumption of reducing agent hydrazine hydrate is 10 times of theoretical value, and reduction temperature is 60 ℃, at 80 ℃ of following vacuum drying 8h, make the target catalyst then; The theoretical value of described reducing agent hydrazine hydrate is calculated by the reaction equation of palladium bichloride salt and reducing agent hydrazine hydrate;
Remaining condition is with claim 4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106068258A (en) * | 2014-03-31 | 2016-11-02 | 国际壳牌研究有限公司 | The production method of Furan and its derivatives |
| CN106132942A (en) * | 2014-03-31 | 2016-11-16 | 国际壳牌研究有限公司 | Method from furfural production furan |
| CN108993496A (en) * | 2018-10-30 | 2018-12-14 | 泰山医学院 | A kind of preparation method for treating dyskinesia drug ropinirole intermediate |
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| CN1308986A (en) * | 2000-11-09 | 2001-08-22 | 中国科学院兰州化学物理研究所 | Catalyst for preparing furan by gas-phase decarbonylation of furaldehyde |
| CN101422738A (en) * | 2007-11-02 | 2009-05-06 | 刘金廷 | Efficient furan preparation catalyst by furfural decarbonylation |
| CN101822982A (en) * | 2008-03-19 | 2010-09-08 | 长春工业大学 | Catalyst for furan production by furfural liquid-phase decarbonylation, preparation method and application method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106068258A (en) * | 2014-03-31 | 2016-11-02 | 国际壳牌研究有限公司 | The production method of Furan and its derivatives |
| CN106132942A (en) * | 2014-03-31 | 2016-11-16 | 国际壳牌研究有限公司 | Method from furfural production furan |
| US9914715B2 (en) | 2014-03-31 | 2018-03-13 | Shell Oil Company | Process for the production of furan and its derivatives |
| US9963437B2 (en) | 2014-03-31 | 2018-05-08 | Shell Oil Company | Process for the production of furan and its derivatives |
| CN108993496A (en) * | 2018-10-30 | 2018-12-14 | 泰山医学院 | A kind of preparation method for treating dyskinesia drug ropinirole intermediate |
| CN108993496B (en) * | 2018-10-30 | 2021-01-15 | 山东第一医科大学(山东省医学科学院) | Preparation method of ropinirole intermediate for treating dyskinesia |
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