CN101940927B - Highly dispersed CuZnTi catalyst for hydrogenation of catalytic maleic anhydride to gamma-butyrolactone and preparation method thereof - Google Patents
Highly dispersed CuZnTi catalyst for hydrogenation of catalytic maleic anhydride to gamma-butyrolactone and preparation method thereof Download PDFInfo
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Abstract
The invention provides a highly dispersed CuZnTi catalyst for hydrogenation of catalytic maleic anhydride to gamma-butyrolactone and a preparation method thereof, belonging to the technical field of catalytic materials. The CuZnTi catalyst is prepared by properly calcining carbonate pillared copper-zinc-titanium houghite used as a catalyst precursor. In the catalyst precursor, the atomic ratio of Cu, Zn and Ti is 0.5:2:1-2.5:2:1. The CuZnTi catalyst comprises the following components in percentage by mass: 11.4-36.2 percent of Cu, 29.5-46.4 percent of Zn and 10.9-17.0 percent of Ti, and the specific surface area of the CuZnTi catalyst is 60.3-125.9m2/g. When the CuZnTi catalyst reacts for 2 hours at the temperature of 200 DEG C under the pressure of 4.0 MPa, the conversion rate of series CuZnTi catalyst for hydrogenation of catalytic maleic anhydride is 88.2-99.6 percent, and the selectivity of the gamma-butyrolactone is 80.7-89.8 percent. The invention has the advantages of being applied to maleic anhydride liquid phase hydrogenation reaction and obtaining higher catalytic activity under lower reaction temperature and pressure.
Description
Technical field
The invention belongs to the catalysis material technical field, a kind of high dispersing copper zinc titanium (CuZnTi) Catalysts and its preparation method of catalysis maleic anhydride hydrogenation system gamma-butyrolacton particularly is provided.
Technical background
The high dispersion metal catalyst is widely used in the catalytic reactions such as dehydrogenation, hydrogenation and reformation, is most important one type of catalyst in petroleum refining and the petrochemical process.It is to be raw material with cis-butenedioic anhydride and derivative thereof that the maleic anhydride hydrogenation legal system is equipped with gamma-butyrolacton, through selecting different catalyst, optionally a kind of important method of synthetic gamma butyrolactone.2003, (Catal.Today, 2003,87,171 such as Jung; J.Mol.Catal.Part A:Chem, 2003,198,297) investigated precious metals pd-Sn/SiO
2Catalyst is 240 ℃ to the catalytic activity of cis-butenedioic anhydride liquid-phase hydrogenatin in reaction temperature, when pressure is 5MPa, reacts after 4 hours, and the yield of gamma-butyrolacton is the highest near 80%.2006, (Industrial Catalysis, 2006 such as Hu Tongjie; 14:41) prepared the CuZnTi catalyst with coprecipitation; Be applied in the cis-butenedioic anhydride gas phase hydrogenation reaction, compare with copper zinc chrome and CuZnAl catalyst, the CuZnTi catalyst has higher activity when reaction temperature is 245 ℃; But when reaction temperature was reduced to 225 ℃, activity obviously descended.Cu: Zn: the Ti atomic ratio is 1: 2: 0.5～1: 2: 2 o'clock, CuO and ZnO and TiO
2Between have strong interaction, catalytic activity is higher, Cu: Zn: the Ti atomic ratio is 2: 2: 0.5～2: 2: 2 o'clock, has free CuO phase in the catalyst, activity of such catalysts and selectivity decline.This is because be difficult to form strong interaction between active metal component and the carrier; And high-temperature roasting also causes metal ion transport easily and form big crystal grain; Both of these case causes in the catalyst metal active constituent dispersiveness relatively poor easily, thereby has influence on the performance of catalyst.
At present, preparation high-dispersion loading type metallic catalyst receives the increasingly extensive concern of people, and the lamellar precursor method is one of important method for preparing in recent years the high-dispersion loading type metallic catalyst.Hydrotalcite (Layered DoubleHydroxies is abbreviated as LDH) is to receive one type of novel inorganic functional material that the researcher widely pays close attention in recent years.Can obtain through the roasting of LDH presoma appropriateness that particle is little, specific area big, the high-dispersion loading type metal composite oxide catalyst of Heat stability is good.This type of catalyst has shown good prospects for application (Catal.Today, 1991,11:173 in heterogeneous catalytic reaction; Appl.Clay Sci, 1999,14:161).
People such as Cordier are in U.S. Pat P 6005145, and having described with nickeliferous LDH is the process that presoma prepares metallic catalyst, and the application of this metallic catalyst in the nitro-aromatic preparing aromatic amine by catalytic hydrogenation.At first, pass through further high-temperature roasting then, obtain the high-dispersion loading type metallic catalyst, at last at H through synthetic LDH presoma with even distribution metal active constituent
2High temperature reduction makes activating catalyst under the atmosphere.This metallic catalyst is applied to catalysis nitro-aromatic hydrogenation preparing arylamine reaction, has than higher active and stable of traditional Raney Raney nickel.People (Mater.Chem.Phys., 2004,87:402 such as Zhang in 2004; Colloids Surfaces A; 2004; 244:169) prepared a series of copper zinc-aluminium hydrotalcite, obtain the copper-based catalysts of high dispersive after the calcining, wherein Cu: Zn: the Al atomic ratio is that 1: 1: 1 catalyst shows the highest catalytic activity in the phenol liquid phase oxidation reaction.
So far, not useful as yet stratiform precursor methods prepares high dispersive CuZnTi catalyst and is applied to the report that cis-butenedioic anhydride liquid-phase hydrogenatin is reacted.
Summary of the invention
The objective of the invention is to carry a kind of high dispersing copper zinc titanium (CuZnTi) Catalysts and its preparation method of catalysis maleic anhydride hydrogenation system gamma-butyrolacton.With carbonate intercalation copper zinc titanium hydrotalcite is catalyst precursor, after appropriate roasting, obtains high dispersive CuZnTi catalyst, is applied to cis-butenedioic anhydride liquid-phase hydrogenatin reaction, under lower reaction temperature and pressure, has obtained advantages of high catalytic activity.
CuZnTi catalyst provided by the present invention be by carbonate intercalation copper zinc titanium hydrotalcite as catalyst precursor, after appropriate roasting, obtain.This catalyst is applicable to the maleic anhydride hydrogenation reaction.
Cu: Zn in the prepared catalyst precursor of the present invention: the Ti atomic ratio is 0.5: 2: 1～2.5: 2: 1.The quality percentage composition of each component is in the CuZnTi catalyst:
The content of Cu is 11.4%～36.2%
The content of Zn is 29.5%～46.4%
The content of Ti is 10.9%～17.0%
The specific area of CuZnTi catalyst is 60.3～125.9m
2/ g.
At reaction condition is 200 ℃, when pressure is 4.0MPa, reacts 2 hours, and the conversion ratio of serial CuZnTi catalyst maleic anhydride hydrogenation is 88.2%～99.6%, and the selectivity of gamma-butyrolacton is 80.7%～89.8%.
Preparation of catalysts method of the present invention is, prepares catalyst precursor carbonate intercalation copper zinc titanium hydrotalcite with two coprecipitations of dripping earlier, and 350 ℃ of roastings of warp make high dispersive CuZnTi catalyst, then at the gaseous mixture (H of hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute) in, to obtain the activated centre be Cu in 260 ℃ of above-mentioned CuZnTi catalyst of reduction
0Activating catalyst.Concrete preparation process is:
(1) preparation of catalyst precursor:
Soluble-salt and TiCl with a certain amount of Cu and Zn
4Hydrochloric acid solution (TiCl
4Hydrochloric acid solution consist of V
TiCl4: V
HCl=2: 3) be dissolved in the lump and be mixed with mixing salt solution A, wherein Cu in the deionized water
2+Concentration be 0.05～0.3 mol, Zn
2+Concentration be 0.2 mol, Ti
4+Concentration be 0.1 mol; NaOH is dissolved in the aqueous slkali B that is mixed with 1.7 mol in the deionized water; In addition with anhydrous Na
2CO
3Be dissolved in the Na that is mixed with 0.2 mol in the deionized water
2CO
3Solution (100mL) changes in the 500mL four-hole boiling flask, under room temperature and stirring condition, mixing salt solution A and aqueous slkali B is added drop-wise in the four-hole bottle with the speed of 2 ml/min simultaneously, and the pH that the dropping process remains solution is 7.5～8.5; A dropwises when mixing salt solution, and slurries crystallization 24 hours in 80 ℃～85 ℃ waters bath with thermostatic control is cooled to room temperature; Products therefrom with deionized water centrifuge washing 3 times after; In 60 ℃ of vacuum drying 24 hours, obtain catalyst precursor carbonate intercalation copper zinc titanium hydrotalcite, be designated as CuZnTi-LDH.
(2) Preparation of catalysts:
With the catalyst precursor CuZnTi-LDH that obtains, in tube furnace, be warming up to 300-350 ℃ with 5-10 ℃/minute, roasting 2 hours obtains corresponding high dispersive CuZnTi catalyst, again with the gaseous mixture (H of this CuZnTi catalyst at hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute) in, obtaining the activated centre in 260 ℃ of reduction is Cu
0Activating catalyst.
The specific embodiment is following:
Embodiment 1
Accurately take by weighing 4.83gCu (NO
3)
23H
2O (0.02mo1), 11.90gZn (NO
3)
26H
2O (0.04mol) and 6.0mL TiCl
4Hydrochloric acid solution (TiCl (0.02mol)
4Hydrochloric acid solution consist of V
TiCl4: V
HCl=2: 3) be dissolved in the deionized water of 200mL, be mixed with mixing salt solution A, wherein CU
2+Concentration be 0.2 mol, Zn
2+Concentration be 0.2 mol, Ti
4+Concentration be 0.1 mol; The NaOH (0.2mol) that other takes by weighing 8g is dissolved in the deionized water of 120mL, is mixed with the aqueous slkali B of 1.7 mol; Take by weighing 2.12g (0.02mol) anhydrous Na
2CO
3Be dissolved in the deionized water of 100mL, be mixed with the Na of 0.2 mol
2CO
3Solution changes in the 500mL four-hole boiling flask, under room temperature and stirring condition, mixing salt solution A and aqueous slkali B is added drop-wise in the four-hole bottle with the speed of 2 ml/min simultaneously, and the pH that the dropping process remains solution is 8.0.After mixing salt solution A dropwises; Slurries crystallization 24 hours in 80 ℃ of waters bath with thermostatic control is cooled to room temperature, products therefrom with deionized water centrifuge washing 3 times after; In 60 ℃ of vacuum drying 24 hours, obtain catalyst precarsor CuZnTi-LDH (Cu: Zn: the Ti atomic ratio is 1: 2: 1).With the catalyst precarsor that obtains, in tube furnace, be warming up to 300 ℃ with 10 ℃/minute, roasting 2 hours obtains corresponding high dispersive CuZnTi catalyst, again with the gaseous mixture (H of this CuZnTi catalyst at hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute) in, obtaining the activated centre in 260 ℃ of reduction is Cu
0Activating catalyst.
Through characterizing the quality percentage composition that obtains Cu in this CuZnTi catalyst is 19.9%, and the quality percentage composition of Zn is 40.4%, and the quality percentage composition of Ti is 14.9%, and specific area is 114.3m
2/ g.At reaction condition is 200 ℃, when pressure is 4.0MPa, reacts 2 hours, and the conversion ratio of this CuZnTi catalyst maleic anhydride hydrogenation is 99.4%, and the selectivity of gamma-butyrolacton is 81.0%.
Embodiment 2
Accurately take by weighing 0.86g (0.005mol) CuCl
22H
2O, 2.72g (0.02mol) ZnCl
2With 3.0mL TiCl
4Hydrochloric acid solution (TiCl
4Hydrochloric acid solution consist of V
TiCl4: V
HCl=2: 3) be dissolved in the deionized water of 200mL, be mixed with mixing salt solution A, wherein Cu
2+Concentration be 0.05 mol, Zn
2+Concentration be 0.2 mol, Ti
4+Concentration be 0.1 mol; The NaOH (0.2mol) that other takes by weighing 8g is dissolved in the deionized water of 120mL, is mixed with the aqueous slkali B of 1.7 mol; Take by weighing 2.12g (0.02mol) anhydrous Na
2CO
3Be dissolved in the deionized water of 100mL, be mixed with the Na of 0.2 mol
2CO
3Solution changes in the 500mL four-hole boiling flask, under room temperature and stirring condition, mixing salt solution A and aqueous slkali B is added drop-wise in the four-hole bottle with the speed of 2 ml/min simultaneously, and the pH that the dropping process remains solution is 7.5.After mixing salt solution A dropwises; Slurries crystallization 24 hours in 80 ℃ of waters bath with thermostatic control is cooled to room temperature, products therefrom with deionized water centrifuge washing 3 times after; In 60 ℃ of vacuum drying 24 hours, obtain catalyst precarsor CuZnTi-LDH (Cu: Zn: the Ti atomic ratio is 0.5: 2: 1).With the catalyst precarsor that obtains, in tube furnace, be warming up to 350 ℃ with 5 ℃/minute, roasting 2 hours obtains corresponding high dispersive CuZnTi catalyst, again with the gaseous mixture (H of this CuZnTi catalyst at hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute) in, obtaining the activated centre in 260 ℃ of reduction is Cu
0Activating catalyst.
Through characterizing the quality percentage composition that obtains Cu is 11.4%, and the quality percentage composition of Zn is 46.4%, and the quality percentage composition of Ti is 17.0%, and specific area is 60.3m
2/ g.At reaction condition is 200 ℃, when pressure is 4.0MPa, reacts 2 hours, and the conversion ratio of this CuZnTi catalyst maleic anhydride hydrogenation is 88.2%, and the selectivity of gamma-butyrolacton is 89.8%.
Embodiment 3
Accurately take by weighing 4.85g (0.02mol) Cu (NO
3)
23H
2O, 5.95g (0.02mol) Zn (NO
3)
26H
2O and 3.0mL TiCl
4Hydrochloric acid solution (TiCl
4Hydrochloric acid solution consist of V
TiCl4: V
HCl=2: 3) be dissolved in the deionized water of 200mL, be mixed with mixing salt solution A, wherein Cu
2+Concentration be 0.2 mol, Zn
2+Concentration be 0.2 mol, Ti
4+Concentration be 0.1 mol; The NaOH (0.2mol) that other takes by weighing 8g is dissolved in the deionized water of 120mL, is mixed with the aqueous slkali B of 1.7 mol; Take by weighing 2.12g (0.02mol) anhydrous Na
2CO
3Be dissolved in the deionized water of 100mL, be mixed with the Na of 0.2 mol
2CO
3Solution changes in the 500mL four-hole boiling flask, under room temperature and stirring condition, mixing salt solution A and aqueous slkali B is added drop-wise in the four-hole bottle with the speed of 2 ml/min simultaneously, and the pH that the dropping process remains solution is 8.0.After mixing salt solution A dropwises; Slurries crystallization 24 hours in 85 ℃ of waters bath with thermostatic control is cooled to room temperature, products therefrom with deionized water centrifuge washing 3 times after; In 60 ℃ of vacuum drying 24 hours, obtain catalyst precarsor CuZnTi-LDH (Cu: Zn: the Ti atomic ratio is 2: 2: 1).With the catalyst precarsor that obtains, in tube furnace, be warming up to 320 ℃ with 10 ℃/minute, roasting 2 hours obtains corresponding high dispersive CuZnTi catalyst, again with the gaseous mixture (H of this CuZnTi catalyst at hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute) in, obtaining the activated centre in 260 ℃ of reduction is Cu
0Activating catalyst.
Through characterizing the quality percentage composition that obtains Cu is 31.8%, and the quality percentage composition of Zn is 32.3%, and the quality percentage composition of Ti is 11.9%, and specific area is 125.9m
2/ g.At reaction condition is 200 ℃, when pressure is 4.0MPa, reacts 2 hours, and the conversion ratio of this CuZnTi catalyst maleic anhydride hydrogenation is 99.6%, and the selectivity of gamma-butyrolacton is 83.3%.
Embodiment 4
Accurately take by weighing 3.62g (0.015mol) Cu (NO
3)
23H
2O, 5.95g (0.02mol) Zn (NO
3)
26H
2O and 3.0mL TiCl
4Hydrochloric acid solution (TiCl
4Hydrochloric acid solution consist of V
TiCl4: V
HCl=2: 3) be dissolved in the deionized water of 200mL, be mixed with mixing salt solution A, wherein Cu
2+Concentration be 0.15 mol, Zn
2+Concentration be 0.2 mol, Ti
4+Concentration be 0.1 mol; The NaOH (0.2mol) that other takes by weighing 8g is dissolved in the deionized water of 120mL, is mixed with the aqueous slkali B of 1.7 mol; Take by weighing 2.12g (0.02mol) anhydrous Na
2CO
3Be dissolved in the deionized water of 100mL, be mixed with the Na of 0.2 mol
2CO
3Solution changes in the 500mL four-hole boiling flask, under room temperature and stirring condition, mixing salt solution A and aqueous slkali B is added drop-wise in the four-hole bottle with the speed of 2 ml/min simultaneously, and the pH that the dropping process remains solution is 8.5.After mixing salt solution A dropwises; Slurries crystallization 24 hours in 80 ℃ of waters bath with thermostatic control is cooled to room temperature, products therefrom with deionized water centrifuge washing 3 times after; In 60 ℃ of vacuum drying 24 hours, obtain catalyst precarsor CuZnTi-LDH (Cu: Zn: the Ti atomic ratio is 1.5: 2: 1).With the catalyst precarsor that obtains, in tube furnace, be warming up to 350 ℃ with 8 ℃/minute, roasting 2 hours obtains corresponding high dispersive CuZnTi catalyst, again with the gaseous mixture (H of this CuZnTi catalyst at hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute) in, obtaining the activated centre in 260 ℃ of reduction is Cu
0Activating catalyst.
Through characterizing the quality percentage composition that obtains Cu is 26.5%, and the quality percentage composition of Zn is 35.5%, and the quality percentage composition of Ti is 13.3%, and specific area is 66.5m
2/ g.In reaction temperature is 200 ℃, when pressure is 4.0MPa, reacts 2 hours, and the conversion ratio of this CuZnTi catalyst maleic anhydride hydrogenation is 99.3%, and the selectivity of gamma-butyrolacton is 80.7%.
Embodiment 5
Accurately take by weighing 6.05g (0.25mol) Cu (NO
3)
23H
2O, 5.95g (0.02mol) Zn (NO
3)
26H
2O and 3.0mL TiCl
4Hydrochloric acid solution (TiCl
4Hydrochloric acid solution consist of V
TiCl4: V
HCl=2: 3) be dissolved in the deionized water of 200mL, be mixed with mixing salt solution A, wherein Cu
2+Concentration be 0.25 mol, Zn
2+Concentration be 0.2 mol, Ti
4+Concentration be 0.1 mol; The NaOH (0.2mol) that other takes by weighing 8g is dissolved in the deionized water of 120mL, is mixed with the aqueous slkali B of 1.7 mol; Take by weighing 2.12g (0.02mol) anhydrous Na
2CO
3Be dissolved in the deionized water of 100mL, be mixed with the Na of 0.2 mol
2CO
3Solution changes in the 500mL four-hole boiling flask, under room temperature and stirring condition, mixing salt solution A and aqueous slkali B is added drop-wise in the four-hole bottle with 2 ml/min simultaneously, and the pH that the dropping process remains solution is 8.0.After mixing salt solution A dropwises; Slurries crystallization 24 hours in 80 ℃ of waters bath with thermostatic control is cooled to room temperature, products therefrom with deionized water centrifuge washing 3 times after; In 60 ℃ of vacuum drying 24 hours, obtain catalyst precarsor CuZnTi-LDH (Cu: Zn: the Ti atomic ratio is 2.5: 2: 1).With the catalyst precarsor that obtains, in tube furnace, be warming up to 350 ℃ with 10 ℃/minute, roasting 2 hours obtains corresponding high dispersive CuZnTi catalyst, again with the gaseous mixture (H of this CuZnTi catalyst at hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute) in, obtaining the activated centre in 260 ℃ of reduction is Cu
0Activating catalyst.
Through characterize obtain Cu the quality percentage composition be 36.2%, the quality percentage composition of Zn is 29.5%, the quality percentage composition of Ti is 10.9%, specific area is 112.3m
2/ g.In reaction temperature is 200 ℃, when pressure is 4.0MPa, reacts 2 hours, and the conversion ratio of this CuZnTi catalyst maleic anhydride hydrogenation is 99.3%, and the selectivity of gamma-butyrolacton is 81.1%.
Claims (2)
1. the high dispersing copper zinc titanium catalyst of a catalysis maleic anhydride hydrogenation system gamma-butyrolacton is characterized in that, the CuZnTi catalyst be by carbonate intercalation copper zinc titanium hydrotalcite as catalyst precursor, after roasting, obtain; This catalyst is applicable to the maleic anhydride hydrogenation reaction;
Cu in the catalyst precursor: Zn: the Ti atomic ratio is 0.5: 2: 1～2.5: 2: 1;
The quality percentage composition of each component is in the CuZnTi catalyst:
The content of Cu is 11.4%～36.2%
The content of Zn is 29.5%～46.4%
The content of Ti is 10.9%～17.0%
The specific area of CuZnTi catalyst is 60.3～125.9m
2/ g;
At reaction condition is 200 ℃, when pressure is 4.0MPa, reacts 2 hours, and the conversion ratio of serial CuZnTi catalyst maleic anhydride hydrogenation is 88.2%～99.6%, and the selectivity of gamma-butyrolacton is 80.7%～89.8%;
This Preparation of catalysts step is following:
(1) preparation of catalyst precursor:
Soluble-salt and TiCl with a certain amount of Cu and Zn
4Hydrochloric acid solution be dissolved in the lump and be mixed with mixing salt solution A, wherein Cu in the deionized water
2+Concentration be 0.05～0.3 mol, Zn
2+Concentration be 0.2 mol, Ti
4+Concentration be 0.1 mol; NaOH is dissolved in the aqueous slkali B that is mixed with 1.7 mol in the deionized water; In addition with anhydrous Na
2CO
3Be dissolved in the Na that is mixed with 0.2 mol in the deionized water
2CO
3Solution 100mL changes in the 500mL four-hole boiling flask, under room temperature and stirring condition, mixing salt solution A and aqueous slkali B is added drop-wise in the four-hole bottle with 2 ml/min simultaneously, and the pH that the dropping process remains solution is 7.5～8.5; A dropwises when mixing salt solution, and slurries crystallization 24 hours in 80 ℃～85 ℃ waters bath with thermostatic control is cooled to room temperature; Products therefrom with deionized water centrifuge washing 3 times after; In 60 ℃ of vacuum drying 24 hours, obtain catalyst precursor carbonate intercalation copper zinc titanium hydrotalcite, be designated as CuZnTi-LDH;
(2) Preparation of catalysts:
With the catalyst precursor CuZnTi-LDH that obtains; In tube furnace, be warming up to 300-350 ℃ with 5-10 ℃/minute, roasting 2 hours obtains corresponding high dispersive CuZnTi catalyst; Again with this CuZnTi catalyst in the gaseous mixture of hydrogen and nitrogen, obtaining the activated centre in 260 ℃ of reduction is Cu
0Activating catalyst;
TiCl
4Hydrochloric acid solution consist of V
TiCl4: V
HCl=2: 3; H in the mist of hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute.
2. described Preparation of catalysts method of claim 1 is characterized in that preparation process is following:
(1) preparation of catalyst precursor:
Soluble-salt and TiCl with a certain amount of Cu and Zn
4Hydrochloric acid solution be dissolved in the lump and be mixed with mixing salt solution A, wherein Cu in the deionized water
2+Concentration be 0.05～0.3 mol, Zn
2+Concentration be 0.2 mol, Ti
4+Concentration be 0.1 mol; NaOH is dissolved in the aqueous slkali B that is mixed with 1.7 mol in the deionized water; In addition with anhydrous Na
2CO
3Be dissolved in the Na that is mixed with 0.2 mol in the deionized water
2CO
3Solution 100mL changes in the 500mL four-hole boiling flask, under room temperature and stirring condition, mixing salt solution A and aqueous slkali B is added drop-wise in the four-hole bottle with 2 ml/min simultaneously, and the pH that the dropping process remains solution is 7.5～8.5; A dropwises when mixing salt solution, and slurries crystallization 24 hours in 80 ℃～85 ℃ waters bath with thermostatic control is cooled to room temperature; Products therefrom with deionized water centrifuge washing 3 times after; In 60 ℃ of vacuum drying 24 hours, obtain catalyst precursor carbonate intercalation copper zinc titanium hydrotalcite, be designated as CuZnTi-LDH;
(2) Preparation of catalysts:
With the catalyst precursor CuZnTi-LDH that obtains; In tube furnace, be warming up to 300-350 ℃ with 5-10 ℃/minute, roasting 2 hours obtains corresponding high dispersive CuZnTi catalyst; Again with this CuZnTi catalyst in the gaseous mixture of hydrogen and nitrogen, obtaining the activated centre in 260 ℃ of reduction is Cu
0Activating catalyst;
TiCl
4Hydrochloric acid solution consist of V
TiCl4: V
HCl=2: 3; H in the mist of hydrogen and nitrogen
2And N
2Volume ratio be 1: 9, flow velocity is 40mL/ minute.
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| CN105642292B (en) * | 2016-01-30 | 2018-04-03 | 山西大学 | Preparation method for C (Ni) nanocatalyst of maleic anhydride hydrogenation synthesis gamma butyrolactone |
| CN111701608B (en) * | 2020-07-09 | 2021-08-31 | 中国科学院过程工程研究所 | Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite |
| CN113731480B (en) * | 2021-09-07 | 2022-10-18 | 中国科学院大连化学物理研究所 | Reaction catalyst for preparing gamma-butyrolactone by maleic anhydride hydrogenation and its preparation and application |
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Non-Patent Citations (2)
| Title |
|---|
| 张瑞超等.正丁醇作溶剂顺酐在Cu-Zn-Ti催化剂上气相加氢制取四氢呋喃.《应用化学》.2007,第24卷(第11期),第1304-1309页. * |
| 胡童杰等.Cu-Zn-Ti催化剂上顺酐气相催化加氢制备γ-丁内酯.《工业催化》.2006,第14卷(第9期),第41-45页. * |
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