CN1131106C - Catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof - Google Patents
Catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof Download PDFInfo
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- CN1131106C CN1131106C CN 00124999 CN00124999A CN1131106C CN 1131106 C CN1131106 C CN 1131106C CN 00124999 CN00124999 CN 00124999 CN 00124999 A CN00124999 A CN 00124999A CN 1131106 C CN1131106 C CN 1131106C
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Abstract
The present invention relates to a maleic anhydride catalyst made by the oxidation of normal butane and a preparation method thereof. The maleic anhydride catalyst is made from V2O5, H3PO4, ZnSO4, a fourth component selected from Fe, Co, Mo, Ni and Cu and a fifth component selected from Er, Ho, Gd, Pr, Dy and Nd. The V2O5, the H2PO4 and the ZnSO4 are firstly reduced under the action of alcohol during the preparation, and MoO3 and rare earth oxide are subsequently added for continuous reaction to make substrate powder. Then, adhesive and other supplementary material are added, and the maleic anhydride catalyst is made after molding. The catalyst of the present invention has high strength, and has little bed resistance, strong loading capacity, high selectivity and high activity when in use.
Description
The present invention relates to a kind of catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof.It is synthetic with V-P-O series metal oxide Catalysts and its preparation method to the invention particularly relates to a kind of cis-butenedioic anhydride.
As everyone knows, maleic anhydride (abbreviation cis-butenedioic anhydride) is important Organic Chemicals.Be widely used in industry such as unsaturated-resin, coating, food, agricultural chemicals, medicine, weaving at present, market is growing to the demand of cis-butenedioic anhydride, and the output of China's cis-butenedioic anhydride is also increasing rapidly in recent years.
The raw material route and the process of producing cis-butenedioic anhydride have multiple.Since exploitation benzene legal system maleic anhydride unit, be that raw material production cis-butenedioic anhydride is most widely used production method always with the benzene method.But because the price of benzene is more expensive, toxicity is also bigger, and is both uneconomical, also do not meet more and more harsher environmental requirement.Therefore, people to wish to find to be that raw material is produced the not only economy of cis-butenedioic anhydride but also the technology of compliance with environmental protection requirements without benzene always.
Was the above-mentioned shortcoming of the raw material technology of producing cis-butenedioic anhydride for solving traditional with benzene, the technology of raw material system cis-butenedioic anhydride occurred doing with low-cost C-4-fraction (normal butane), and has become the new trend that cis-butenedioic anhydride is produced, and had realized suitability for industrialized production in 1975.Company such as Monsanto, Petro-tex successively reconstructs or be newly-built is the device of raw material with the normal butane.Along with the development of petrochemical industry provides a large amount of cheap normal butanes, normal butane toxicity unlike benzene is big, and butane is produced the device of cis-butenedioic anhydride and benzene method roughly the same, originally adopt the company of benzene method can on original device basic, turn to the n butane oxidation method rapidly, these factors have been impelled developing rapidly of n butane oxidation method, and the production method that makes cis-butenedioic anhydride is towards rationally more economically, develop the more favourable direction of environmental protection.But, because the used catalyst of n butane oxidation method technology exists activity on the low side, poor selectivity, shortcomings such as it is little to load, and life cycle is short have increased the use amount of catalyst, reduce the conversion per pass and the certified products yield of this technology, thereby increased production cost greatly.
For solving the above-mentioned shortcoming of traditional n butane oxidation method catalyst for preparing cis-anhydride, Chinese patent 1042701C (Granted publication day 93.11.16, it is for reference to introduce the present invention in full) has proposed a kind of V-P-O series catalysts.The described open middle catalyst of describing is as solvent and reducing agent, H with isobutanol
3PO
4Concentration is 85%, and is third and fourth component with Zn, Er.Be binding agent with modified starch in the catalysis moulding, finished catalyst is a trilobal.
Yet there is following shortcoming in such catalyst:
1) yield of cis-butenedioic anhydride and conversion ratio significantly descend with the increase of load in single column run.
2) at high load capacity (as 2000hr
-1) time catalyst the hot(test)-spot temperature height, and yield and selectivity are all undesirable.
3) bed resistance is big, is difficult to improve catalyst loading, is unfavorable for shifting out of beds heat.
4) catalyst strength is bad, and is easily broken, and shortened catalyst service life.
Therefore, adopt such catalyst to be difficult to adapt to the requirement that high-efficiency and economic ground produces cis-butenedioic anhydride under the high load capacity.
So, an object of the present invention is to provide a kind of high-intensity new catalyst that can under high load capacity, move and have high yield and high conversion.Adopt carbon monoxide-olefin polymeric of the present invention, can reduce bed resistance and be beneficial to heat and shift out, and reduce high load capacity hot(test)-spot temperature down, improve catalyst strength, prolongation catalyst service life.
Another object of the present invention provides a kind of method for preparing above-mentioned catalyst.
Be the used catalyst of n butane oxidation legal system maleic anhydride process that exploitation does not have aforesaid drawbacks, the inventor has carried out intensive research.As a result, the inventor unexpectedly finds:
1) by on the basis of Chinese patent CN1042701C, reselecting suitable active constituent and reselecting the content of each active constituent, can significantly improve activity of such catalysts and selectivity;
2) select suitable water-soluble resin adhesive can improve the intensity of catalyst as binding agent in forming process, be difficult for brokenly, the corresponding raising of the hot(test)-spot temperature that can tolerate has improved the specific surface of catalyst simultaneously to a certain extent, has increased activity of such catalysts;
3) change original trilobal shape into ring-type or semicircular, can reduce bed resistance greatly, improve the mass-and heat-transfer effect, reduce hot(test)-spot temperature, and catalyst is easy to processing;
4) phosphoric acid with higher concentration replaces original 85% phosphoric acid that uses, and can improve activity of such catalysts and selectivity greatly.
Below the present invention is carried out more detailed description.Before disclosure and description catalyst for preparing cis-anhydride by n-butane oxidation of the present invention and preparation method thereof, need point out, the present invention is not limited to the restriction of special construction described herein, method step and material, and these structures, method step and material can change to some extent.
The catalyst of n butane oxidation system maleic anhydride of the present invention comprises embodiment hereinafter described.
The catalyst that comprises the n butane oxidation system maleic anhydride of matrix powder and molding materials, wherein,
Matrix powder comprises:
1)V
2O
5；
2) concentration expressed in percentage by weight is the phosphoric acid of 90-110%;
3) Zn salt is as zinc sulfate, zinc nitrate etc.;
4) a kind of or its mixture of the oxide of rare earth element er, chloride, sulfate, nitrate or carbonate, the oxide of preferred Er;
5) be selected from a kind of or its mixture of oxide, chloride, sulfate, nitrate or the carbonate of metals such as Ho, Gd, Tb, Mo, Nb, Co, Ni, Mn, Fe, the oxide of preferred Mo, Ni, metals such as Mn, Co, the oxide of special preferable alloy Mo;
Molding materials comprises:
1) converted starch;
2) water-soluble resin adhesive;
3) stearic acid
Wherein, the mol ratio of each element is
V∶P∶Zn∶Er∶Me∶O＝1∶.0.5～2.5∶0.01～0.20∶0.001～0.05∶0.001～0.025∶X，
Be preferably 1: .0.9～2.0: 0.01～0.20: 0.005～0.025: 0.005～0.025: X,
More preferably 1: 0.5-1.2: 0.01-0.04: 0.005-0.008: 0.005-0.008: X.
Wherein Me is the 5th) metallic element of component, X is for satisfying the needed oxygen atomicity of other element valence requirement;
Can also use graphite during shaping of catalyst, the weight ratio of each component is: matrix powder: stearic acid: graphite: converted starch: water-soluble resin adhesive=1: 0.01～0.018: 0.01～0.022: 0.033～0.1: 0.2～0.9, preferred 1: 0.01～0.017: 0.01～0.017: 0.033～0.1: 0.2～0.9.
Described converted starch is to be reacted and made by starch and modifier, and the charge ratio of starch and modifier is 1: 0.01～0.50, be preferably 1: 0.05～and 0.30, all by weight; Wherein starch is one or more the mixture in tapioca, farina, cornstarch, wheaten starch or the rice starch; Modifier is one or more the mixture in formaldehyde, epoxychloropropane, POCl3, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), metaphosphate, sodium sulphate, niter cake, the cis-butenedioic anhydride.
Described water-soluble resin adhesive is selected from polyvinyl alcohol resin, one or more of polyacrylic resin, vinyl acetate resin, aldehyde resin, preferably polyethylene alcohol resin.
The molecular weight and the consumption that are applicable to water-soluble resin adhesive of the present invention have no particular limits.Preferred molecular weight of the present invention is the polyvinyl alcohol resin of 1500-2000.The consumption of water-soluble resin adhesive can change in a big way, depends on the catalyst strength that hope obtains.
The present invention also provides the preparation method of carbon monoxide-olefin polymeric of the present invention, comprising: use V
2O
5With concentration expressed in percentage by weight be that the phosphoric acid of 90-110% is parent stock, the oxide that adds Zn salt and Er, chloride, sulfate, nitrate or carbonate a kind of or their mixture, and be selected from Ho, Gd, Tb, Mo, Nb, Co, Ni, Mn, the oxide of metals such as Fe, chloride, sulfate, the 5th component of a kind of or its mixture of nitrate or carbonate, in alcohols, carry out redox reaction in 90 ± 4 ℃, from reactant mixture, separate and obtain matrix powder, then, adopting converted starch and water-soluble resin adhesive is binding agent, the employing stearic acid is a pore creating material, mix after moulding makes catalyst with matrix powder;
The mol ratio of each element be V: P: Zn: Er: Me: O=1: .0.5～2.5: 0.01～0.20: 0.001～0.05: 0.001～0.025: X wherein Me be the metallic element of the 5th component, X is for satisfying the needed oxygen atomicity of other element valence requirement;
The weight ratio of each component is in the shaping of catalyst process:
Matrix powder: stearic acid: graphite: converted starch: water-soluble resin adhesive=1: 0.04～0.018: 0.0058～0.0220: 0.01～0.25: 0.001～0.005.
In a specific embodiments of the present invention, catalyst of the present invention can prepare according to following processing step:
(A) preparation of matrix powder:
With V
2O
5, H
3PO
4(concentration is 90-110%), zinc salt are (as ZnSO
4) join in the there-necked flask, and add alcohol compound (as isobutanol) as solvent, and add sulfuric acid, under agitation be heated to 90 ± 4 ℃ of backflows, V in the course of reaction
2O
5Progressively be reduced to turquoise, react after 6 hours, add foregoing the 5th component Me (as metal oxides such as Fe, Co, Mo, Ni, Cu and as Er
2O
3, Ho
2O
3, Gd
2O
3, Tb
2O
3, Dy
2O
3, Ce
2O
3Rare earth oxide), continue to reflux.Finish reaction after 5 hours, and material is leached from reactant liquor, and, will leach the thing oven dry, obtain the blue substrate powder with after the alcohol compound washing for several times.
(B) moulding of catalyst:
The molding materials prescription is as follows:
Matrix powder 100 grams
Stearic acid 1 gram
Graphite 1 gram
Polyvinyl alcohol glue 20 grams of converted starch 10 gram number-average molecular weights 1800
Water is an amount of
Above mixing of materials is even, be processed into φ 5 * 5 * 1.5mm-φ 8 * 5 * 5mm after the kneading, the oven dry back is a catalyst prod.
120ML (1200ML) fixed bed reactors of then catalyst being packed into activate, and the activation back is dropped into to run well and produced cis-butenedioic anhydride.
The reaction condition of catalyst:
Air speed is 500-2200 hour
-1, the concentration of normal butane is 1.0-1.6% (volume), and temperature of molten salt is 390-450 ℃, and activation temperature is 300-430 ℃, and soak time is 20-40 hour.Evaluation result: the cis-butenedioic anhydride weight yield is 〉=90%, and conversion ratio is 〉=80%, and selectivity is 67-75%.
As known from the above: catalyst of the present invention adds in V-P-O system can improve activity of such catalysts and selectivity after transition metal and rare earth compound are auxiliary agent, and details see Table 1.
Catalyst of the present invention has following characteristics:
1. prepare the H that catalyst of the present invention adopts
3PO
4Concentration is 90-110%, and activity of such catalysts and selectivity ratios are with the H of 85% concentration
3PO
4The time height.(details see Table 1)
2. compared with prior art, activity of such catalysts of the present invention and stability improve a lot, and under similarity condition, yield can improve about 10 percentage points, and conversion ratio then can improve about 6 percentage points.Bed resistance is reduced to so far by 0.6Mpa.
3. catalyst is a ring-type, can reduce bed resistance and reduce to 0.3Mpa by 0.6Mpa, also reduces hot(test)-spot temperature (corresponding data is referring to table 1) simultaneously, and catalyst is easy to processing.
4. add rare earth as auxiliary agent, can improve activity of such catalysts and selectivity.
5. add in the matrix powder with converted starch and polyvinyl alcohol glue, the catalyst strength height that molds, and be difficult for broken.Improve simultaneously the specific area of catalyst to a certain extent, increased activity of such catalysts.By the following examples of the present invention and corresponding to the Comparative Examples of prior art as can be seen, the vertical intensity of catalyst of the present invention is up to 8.5kg/cm
2, transverse strength is up to 5.5kg/cm
2, and the vertical intensity of the catalyst of tri-lobed only has 3.5kg/cm
2, transverse strength only has 1.1kg/cm
2
The following examples have been done further description to Catalysts and its preparation method of the present invention, and these embodiment are in order to explanation rather than restriction the present invention.
Unless specialize, the physical data in the following examples adopts following method to measure:
Crystalline phase: the NICOLET 710FTIR type spectrometer that database is housed
BET specific area: ASAP2000 type device, N2 absorption method
Pore volume: Autopore III 9410 pore-size distribution analyzers
Most probable bore dia: Autopore III 9410 pore-size distribution analyzers
Transverse strength: the log cabin QCY-602 of Amada Co., Ltd. type intensity measuring device
Vertical intensity: the log cabin QCY-602 of Amada Co., Ltd. type intensity measuring device
Number-average molecular weight: gel permeation chromatograph
Embodiment 1
In a 1000ml there-necked flask that has agitator and a spherical reflux condenser, add 55.76 gram V
2O
5, 4.91 gram ZnSO
47H
2O, 0.883 gram Mo
3., the dense H of 3.99ml
2SO
4Stir, add concentration with the 600ml isobutanol and be 105% H
3PO
4Heating makes temperature rise to 92 ℃, refluxes to add 81.20 gram solution after 1 hour in bottle, refluxed 6 hours, this moment, solution was turquoise, added 0.117 gram bait oxide again in bottle, continued to reflux 3 hours, obtain turquoise suspension, it is cooled to 40 ℃,, filter with Buchner funnel, the filter cake that stays obtains matrix powder with washed filter cake then with the washing of 350ML isobutanol after 90 ℃ of oven dry.
Take by weighing above-mentioned 100 gram matrix powders, hard ester acid lg, graphite lg, modified starch 10g, polyvinyl alcohol glue is an amount of, and water is an amount of, and above mixing of materials is even, mediates the back and be shaped to Φ 5 * 5 * 1.5mm ring-type catalyst prod on banded extruder.
The 120ML fixed bed reactors of then catalyst being packed into activate, and the activation back is dropped into to run well and produced cis-butenedioic anhydride.
The reaction condition of catalyst:
Air speed is 2000 hours
-1, the concentration of normal butane is 1.34% (volume), and hot(test)-spot temperature is 461 ℃, evaluation result: the cis-butenedioic anhydride weight yield is 94.9%, and conversion ratio is 82%.Catalyst specific surface 25.4 meters squared per gram.(measuring the catalyst specific surface) with the BET method
Comparative example 1
Method by CN1042701C embodiment 1 prepares catalyst, and this catalyst is 2000 hours in air speed
-1, the concentration of normal butane is 1.34% (volume), temperature of molten salt is 488 ℃.Evaluation result: the cis-butenedioic anhydride weight yield is 82%, and conversion ratio is 76%.24.4 meters of catalyst specific surfaces
2/ gram.
When estimating in single tube, this catalyst finds to work as air speed from 1000 hours
-1Bring up to 1500 hours
-1, when the concentration of normal butane was brought up to 1.53% (volume) from 134% (volume), hot(test)-spot temperature was 488 ℃, and the cis-butenedioic anhydride weight yield is for dropping to 73% from 82%, and conversion ratio is for to drop to 70% from 76%.
Embodiment 2
Experimental rig, method of operating, feeding quantity and reaction condition are with embodiment 1, and that different is H
3PO
4Concentration be 107%, the results are shown in Table 1 for it.
Comparative example 2
Prepare catalyst by embodiment 1 method, its difference is with concentration to be 85% H
3PO
4, this catalyst is 2000 hours in air speed
-1, the concentration of normal butane is 1.325% (volume), 480 ℃ of hot(test)-spot temperatures, and the cis-butenedioic anhydride weight yield is 82%, conversion ratio is 76%.
Embodiment 3
Experimental rig, method of operating, feeding quantity and reaction condition are with embodiment 1, and different is with 0.46 gram Nb
2O
5Substitute MoO
3, evaluation result is listed in the table 1.Embodiment 4
Experimental rig, method of operating, feeding quantity and reaction condition are with embodiment 1, and different is with 1.785 gram Co (N0
3) 6H
2O replaces MoO
3The results are shown in Table 1 for it.
The cis-butenedioic anhydride weight yield is 93.4%, conversion ratio 81%
Embodiment 5
1) preparation of matrix powder is with embodiment 1
2) shaping of catalyst
The molding materials prescription is as follows:
Matrix powder 100 grams
Stearic acid 1 gram
Graphite 1 gram
Converted starch 10 gram number-average molecular weights are 1800 polyvinyl alcohol glue 20 grams
Water is an amount of
Above mixing of materials is even, mediate the back and on banded extruder, be shaped to Φ 5 * 5 * 1.5mm ring-type.The oven dry back is a catalyst prod.
In the 120ML fixed bed reactors 420 ℃, under air and butane atmosphere, activate, to estimate then, this catalyst physical data is as follows:
Crystalline phase is: (VO)
2P
2O
7
BET specific area: 25.5 meters squared per gram
Pore volume: 0.0115ml/ gram
Most probable bore dia: 532A °
Transverse strength: 5.5 kilograms/(strength detection with Japanese strain formula can shut out log cabin intensity measuring device)
Vertical intensity: 8.5 kilograms/
Evaluation result: the cis-butenedioic anhydride weight yield is 95%, and conversion ratio is 83%.
Comparative example 3
Prepare matrix powder according to embodiment 1 method, according to the method preformed catalyst of embodiment 5, different is without polyvinyl alcohol glue then.
The catalyst physical data is as follows:
Crystalline phase is: (VO)
2P
2O
7
BET specific area: 21.7 meters squared per gram
Pore volume: 0.0117ml/ gram
Most probable bore dia: 530A °
Transverse strength: 1.1 kilograms/
Vertical intensity: 3.5 kilograms/
Evaluation result: the cis-butenedioic anhydride weight yield is 83, and conversion ratio is 76%.
Table 1
Embodiment 6
| Tested number | Raw material ratio | N-C 0 4Concentration | Air speed hr -1 | Focus ℃ | Conversion ratio % | Yield % | Resistance Mpa |
| Embodiment 1 | V-P-Zn-Mo-Er 1∶1.22∶0.04∶∶0.02∶0.001 | 1.34 | 2000 | 461 | 82 | 94.9 | 0.3 |
| Comparative example 1 | V-P-Zn-Er 1∶1.22∶∶0.05∶0.001 | 1.36 | 2000 | 488 | 76 | 83 | 0.6 |
| Embodiment 2 * | V-P-Zn-Mo-Er 1∶1.22∶0.04∶0.02∶0.001 | 1.345 | 2000 | 465 | 8 | 92 | 0.3 |
| Comparative example 2 * | V-P-Zn-Mo-Er 1∶1.22∶0.04∶0.02∶0.001 | 1.32 | 2000 | 480 | 76 | 82 | 0.6 |
| Embodiment 3- | V-P-Zn-Nb-Er 1∶1.22∶0.04∶0.02∶0.001 | 1.34 | 2000 | 475 | 83 | 91 | 0.3 |
| Embodiment 4 | V-P-Zn-Co-Er 1∶1.22∶0.04∶0.02∶0.001 | 1.32 | 2000 | 474 | 86 | 53 | 0.3 |
| Embodiment 6 | V-P-Zn-Mn-Er 1∶1.2∶0.04∶0.01∶0.006 | 1.34 | 2000 | 470 | 81 | 93.4 | 0.3 |
| Embodiment 7 | V-P-Zn-Co-Er 1∶1.22∶0.04∶0.01∶0.001 | 1.32 | 2000 | 472 | 80 | 93.4 | 0.3 |
| Embodiment 8 | V-P-Zn-Mo-Er 1∶1.22∶0.04∶∶0.02∶0.001 | 1.55 | 2200 | 461 | 81.7 | 91.73 | 0.4 |
In a 1000ml there-necked flask that has agitator and a spherical reflux condenser, add 65 gram V
2O
5.4.51 gram ZnSO
47H
2O, 1.29 gram MnO
3., the dense H of 4.6ml
2SO
4Stir, add concentration with the 600ml isobutanol and be 105% H
3PO
4Heat makes temperature rise to 92 ℃, refluxes to add 81.20 gram solution after 1 hour in bottle, refluxed 6 hours, this moment, solution was turquoise, added 0.0137 gram bait oxide again in bottle, continued to reflux 3 hours, obtain turquoise suspension, it is cooled to 40 ℃,, filter with Buchner funnel, the filter cake that stays obtains matrix powder with washed filter cake then with the washing of 350ML isobutanol after 90 ℃ of oven dry.
Take by weighing above-mentioned 100 gram matrix powders, hard ester acid 1g, graphite 1g, modified starch 10g, polyvinyl alcohol glue is an amount of, and water is an amount of, and above mixing of materials is even, mediates the back and be shaped to Φ 5 * 5 * 1.5mm ring-type catalyst prod on banded extruder.
The 120ML fixed bed reactors of then catalyst being packed into activate, and the activation back is dropped into to run well and produced cis-butenedioic anhydride.
The reaction condition of catalyst: air speed is 2000 hours
-1, the concentration of normal butane is 1.34% (volume), temperature of molten salt is 461 ℃, evaluation result: the cis-butenedioic anhydride weight yield is 93.4%, conversion ratio 81%.Catalyst specific surface 24.4 meters squared per gram.
Embodiment 7
Experimental rig, method of operating, feeding quantity and reaction condition are with embodiment 4, and different is with 1.165 gram Co (NO
3) 6H
2O replaces MoO
3Its as a result the cis-butenedioic anhydride weight yield be 93.4%, conversion ratio 80%.
Embodiment 8Experimental rig is single tube (1200ML), and method for preparing catalyst and reaction condition are with embodiment 1, and different is by 1.2L scale preparation catalyst, reaction result such as table 1.
Embodiment 91) preparation of matrix powder is with embodiment 12) the shaping of catalyst method is with embodiment 5
The molding materials prescription is as follows:
Matrix powder 300 grams
Stearic acid 5 grams
Graphite 5 grams
Converted starch 10 gram number-average molecular weights are 1800 polyvinyl alcohol glue 270 grams
Water is an amount of
Above mixing of materials is even, mediate the back and on banded extruder, be shaped to Φ 5 * 5 * 1.5mm ring-type.The oven dry back is a catalyst prod.
In the 120ML fixed bed reactors 420 ℃, under air and butane atmosphere, activate, to estimate then, this catalyst physical data is as follows:
Crystalline phase is: (VO)
2P
2O
7
BET specific area: 25.5 meters squared per gram
Pore volume: 0.0125ml/ gram
Most probable bore dia: 532A °
Transverse strength: 6.5 kilograms/
Vertical intensity: 9.5 kilograms/
The cis-butenedioic anhydride weight yield is 92.4%, conversion ratio 80%.
Claims (9)
1, a kind of carbon monoxide-olefin polymeric that is used for n butane oxidation system maleic anhydride, said composition comprises matrix powder and molding materials, wherein,
Matrix powder comprises:
1)V
2O
5；
2) concentration expressed in percentage by weight is the phosphoric acid of 90-110%;
3) Zn salt;
4) oxide of rare earth element er, chloride, sulfate, nitrate or carbonate a kind of or their mixture;
5) be selected from oxide, chloride, sulfate, nitrate or carbonate a kind of of Ho, Gd, Tb, Mo, Nb, Co, Ni, Mn, Fe or their mixture;
Molding materials comprises:
1) converted starch;
2) water-soluble resin adhesive;
3) stearic acid;
The mol ratio of each element is V: P: Zn: Er: Me: O=1: 0.5～2.5: 0.01～0.20: 0.001～0.05: 0.001～0.025: X, wherein Me is the 5th) metallic element of component, X is for satisfying the needed oxygen atomicity of other element valence requirement.
2, carbon monoxide-olefin polymeric according to claim 1, the mol ratio of each component is: V: P: Zn: Er: Me: O=1: .0.9～2.0: 0.01～0.20: 0.005～0.025: 0.005～0.025: X.
3, carbon monoxide-olefin polymeric according to claim 1, the mol ratio of each component is: V: P: Zn: Er: Me: O=1: 0.5-1.2: 0.01-0.04: 0.005-0.008: 0.005-0.008: X.
4, carbon monoxide-olefin polymeric according to claim 1 also uses graphite when it is characterized in that shaping of catalyst, the weight ratio of each component is:
Matrix powder: stearic acid: graphite: converted starch: water-soluble resin adhesive=1: 0.01～0.018: 0.01～0.022: 0.033～0.1: 0.2～0.9.
5, carbon monoxide-olefin polymeric according to claim 4, the weight ratio of each component is when it is characterized in that shaping of catalyst:
Matrix powder: stearic acid: graphite: converted starch: water-soluble resin adhesive=1: 0.01～0.017: 0.01～0.017: 0.033～0.1: 0.2～0.9.
6, according to claim 4 or 5 described carbon monoxide-olefin polymerics, it is characterized in that described converted starch is to be reacted and made by starch and modifier, starch and modifier charge ratio by weight is 1: 0.01～0.50; Wherein starch is one or more the mixture in tapioca, farina, cornstarch, wheaten starch or the rice starch; Modifier is one or more the mixture in formaldehyde, epoxychloropropane, POCl3, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), metaphosphate, sodium sulphate, niter cake, the cis-butenedioic anhydride.
7,, it is characterized in that described starch and modifier charge ratio by weight is 1: 0.05～0.30 according to the carbon monoxide-olefin polymeric of claim 6.
8,, it is characterized in that described water-soluble resin adhesive is selected from polyacrylic resin, vinyl acetate resin, aldehyde resin, one or more of polyvinyl alcohol resin according to claim 4 or 5 described carbon monoxide-olefin polymerics.
9, according to the preparation method of the carbon monoxide-olefin polymeric of one of claim 1-4, it is characterized in that: use V
2O
5With concentration expressed in percentage by weight be that the phosphoric acid of 90-110% is parent stock, the oxide that adds Zn salt and Er, chloride, sulfate, nitrate or carbonate a kind of or their mixture, and be selected from Ho, Gd, Tb, Mo, Nb, Co, Ni, Mn, the oxide of Fe, chloride, sulfate, a kind of or its mixture of nitrate or carbonate the 5th) component, in alcohols, carry out redox reaction in 90 ± 4 ℃, from reactant mixture, separate and obtain matrix powder, then, adopting converted starch and water-soluble resin adhesive is binding agent, the employing stearic acid is a pore creating material, mix after moulding makes catalyst with matrix powder.
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| CN103691466B (en) * | 2012-09-27 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of catalyst precursor and preparation method thereof and catalyst and application thereof |
| CN103691467B (en) * | 2012-09-27 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of Catalysts and its preparation method and application |
| CN106311300A (en) * | 2015-06-24 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst used for preparation of maleic anhydride through oxidation of butane, and preparation and application methods thereof |
| CN108101873A (en) * | 2016-11-24 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of method that n butane oxidation prepares cis-butenedioic anhydride |
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2000
- 2000-09-29 CN CN 00124999 patent/CN1131106C/en not_active Expired - Lifetime
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