CN1034476C - Synthetic methyl isobutyl acetone molecular sieve catalyst and its preparation method - Google Patents
Synthetic methyl isobutyl acetone molecular sieve catalyst and its preparation method Download PDFInfo
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- CN1034476C CN1034476C CN91105999A CN91105999A CN1034476C CN 1034476 C CN1034476 C CN 1034476C CN 91105999 A CN91105999 A CN 91105999A CN 91105999 A CN91105999 A CN 91105999A CN 1034476 C CN1034476 C CN 1034476C
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Abstract
The present invention relates to a catalyst which uses a ZSM-5 molecular sieve synthesized by a non-amine method as a carrier, metal Pd as an active component and metal Cu as an auxiliary agent. The use of the molecular sieve as a carrier can lower cost and reduce pollution. Meanwhile, the use of the metal Cu as the auxiliary agent can effectively lower the content of the active component Pd. The optimum range of the catalyst metal content of the present invention is 0.15 to 0.25% of Pd and 0.15 to 0.25% of Cu. The catalyst has the selectivity of 95 to 98% and the acetone conversion rate of 36 to 42%.
Description
The present invention relates to a kind of containing metal molecular sieve catalyst and method for making thereof, especially relate to a kind of metallic molecular sieve catalyst and method for making thereof that is used for acetone one-step method synthesize methyl-isobutyl ketone.
Methyl iso-butyl ketone (MIBK) (hereinafter to be referred as MIBK) is a kind of medium-boiling solvent, can be as the solvent of NC Nitroncellulose, varnish and coating resin (vinyl, propenyl polymer), also be the efficient solvent of separating inorganic salts, also can be as the extractant of rare earth element.The catalyst that utilizes the synthetic MIBK of acetone one-step method to use, at present extensively employing and industrialized be palladium-resin type catalyst, the advantage of this catalyst is a low price, and higher activity and selectivity are arranged.But the poor heat stability of this catalyst exists palladium to run off and sulfonate radical comes off, and the control of operating condition requires deficiencies such as harshness.
United States Patent (USP) 4, the catalyst of introducing in 339,606 is the molecular sieve catalyst of containing metal palladium (Pd), i.e. Pd/ZSM-5 type catalyst, can overcome the weak point of Pd/ resin type catalyst, and peer-level active, that selectivity can reach the Pd-resin type catalyst.But the ZSM-5 molecular sieve that Pd/ZSM-5 type catalyst is adopted is with there being the amine method synthetic, thereby in roasting process, can produce aminate and nitrogen oxide contaminated environment like this, and there is the cost of the synthetic type ZSM 5 molecular sieve of amine method higher, the active constituent that is adopted is the one-component metal, and active metallic content is higher relatively.
The objective of the invention is weak point, provide that a kind of carrier cost is low, the relatively low Catalysts and its preparation method of active component (noble metal) content at the Pd/ZSM-5 catalyst, and no aminate and nitrogen oxides pollution environment in the preparation process.
According to Chinese patent CN8510032B, adopt the synthetic type ZSM 5 molecular sieve of non-amine method.During the non-amine method synthesis of molecular sieve, needn't use any organic additive reagent, directly use waterglass, inorganic salts, aluminium salt (or aluminate) to synthesize, this has just reduced production cost widely, has also solved the problem of environmental pollution that organic amine causes.In addition, owing to do not contain organic amine, the synthetic type ZSM 5 molecular sieve of non-amine method can be without roasting, directly carries out ion-exchange and produces various catalyst.Therefore, to adopt the synthetic type ZSM 5 molecular sieve of non-amine method be the carrier of catalyst in the present invention.
Because the metal Pd as the catalyst activity component belongs to noble metal, the content height of metal Pd, then the cost of catalyst is also high.Another object of the present invention is to seek a kind of element as auxiliary agent, with the content of suitable reduction metal active constituent Pd.Catalyst in the experiment adopts IB family element as auxiliary agent, especially is auxiliary agent with Cu, can reduce the content of metal effectively, can improve activity of such catalysts and stability.
Therefore, it is carrier that the present invention adopts non-amine method ZSM-5, and metal Pd is an active component, and metal Cu is an auxiliary agent.
Catalyst of the present invention is that the ZSM-5 molecular sieve that synthesizes with non-amine method is a carrier, is active component with the metal Pd, and IB family element is an auxiliary agent, is auxiliary agent with metal Cu especially, with Al (OH)
3Be adhesive.Wherein the content range of metal Pd is 0.01-0.4% (weight), and the content of metal Cu is 0.01-0.4% (weight), and the content of metal Pd is preferably 0.15-0.25% (weight), and the content of metal Cu is preferably 0.15-0.25% (weight), Al
2O
3Content be 20-30% (weight).
Catalyst preparation process of the present invention is that the NaZSM-5 type molecular sieve that non-amine method is synthetic carries out ion-exchange with inorganic acid, gets HZSM-5 type molecular sieve, then the HZSM-5 molecular sieve is made slurries, these slurries and PdCl
2, CuCl
2Ammonia spirit mix, carry out ion-exchange after, washing is to there not being Cl
-, filtration then, dry, roasting add with Al
2O
3The weight meter accounts for the 20-30%Al (OH) of catalyst weight
3Adhesive, behind the extruded moulding, drying is handled, roasting, promptly draws the present invention's catalyst after 550 ℃-600 ℃ high-temperature water vapor is handled.
Preparation of catalysts method of the present invention is finished as follows.1, the preparation of no amine type HZSM-5 molecular sieve
The NaZSM-5 molecular sieve that a certain amount of non-amine method is synthetic carries out ion-exchange with inorganic acid.The inorganic acid that adopts is nitric acid, sulfuric acid, hydrochloric acid etc., is preferably hydrochloric acid; The concentration of inorganic acid is 0.2-1.0N, preferably 0.2-0.4N.The exchange temperature is controlled at 90-95 ℃, and be 1 hour each swap time, exchanges altogether three times, and the washing of exchange back is to there not being Cl
-, promptly get the HZSM-5 molecular sieve after drying, the roasting then.2, PdCl
2, CuCl
2The preparation of solution
Take by weighing a certain amount of PdCl respectively
2And CuCl
2Add in the ammonia spirit of PH=10-12 PdCl respectively
2, CuCl
2Concentration be all 2% (weight).With PdCl
2Ammonia spirit and CuCl
2Ammonia spirit be heated to 75-80 ℃, constant temperature is transparent to solution.3, with PdCl
2Ammonia spirit and CuCl
2Ammonia spirit dropwise add in the HZSM-5 molecular sieve pulp, the solid-to-liquid ratio of molecular sieve pulp is 1: 2, adds the PH=10-12 that ammoniacal liquor is regulated slurries, PdCl
2And CuCl
2Addition press Pd
2+, Cu
2+Exceed the contained Pd of actual catalyst
2+, Cu
2+The 20-30% of amount calculate (the i.e. Pd of Jia Ruing
2+, Cu
2+Total amount is than the Pd in the exchange
2+, Cu
2+Total amount will exceed 20-30% (weight)).The NH that adds 1% (weight) simultaneously
4Cl (in the catalyst butt) is as the absorption competition agent.Mixed liquor is warming up to 90-95 ℃, carries out ion-exchange, be 1 hour swap time, and the washing of exchange back is to there not being Cl
-, filtration, drying, adding are with Al
2O
3Weight accounts for the Al (OH) of catalyst weight meter 20-30%
3Adhesive, behind the extruded moulding, drying handles, after 550-600 ℃ high-temperature water vapor is handled the catalyst that promptly gets the present invention.
The present invention has following advantage.1, because the ZSM-5 molecular sieve that has adopted non-amine method to synthesize is the carrier of catalyst, thereby can reduce the cost of catalyst, can eliminate the pollution to environment such as aminate, in addition, because non-amine method ZSM-5 molecular sieve does not contain amine, therefore can directly molecular screen primary powder be carried out acid treatment, can reduce the bakes to burn the article process.2, catalyst of the present invention is an auxiliary agent owing to having added with IB family element, especially added copper, thereby adjusted the electronic property of palladium, make copper be in the palladium atom around, thereby between the palladium atom, form barrier, make it both to make palladium be reduced to metallic state, also be difficult for each other gathering, thereby increased the decentralization of palladium and reduced the chance of green coke.3, catalyst of the present invention is owing to add auxiliary agent, precious metals pd content as the catalyst activity component is reduced, the palladium content of the Pd/ZSM-5 catalyst of the U.S. is 0.5% (weight), and the palladium in the PdCu/ZSM-5 catalyst that the present invention makes (0.4% (weight), and selectivity and conversion ratio and Pd/ZSM-5 are suitable.4, because employing ZSM-5 molecular sieve is a carrier, because of it has hydrophobicity, it is the dimerization dehydration that thereby this process of making had both made, also can keep its long-term operation (reaching not inactivation of 2000 little fashion) also not pulverize, and keep its high strength, turn round and tore a rear catalyst intensity in 2000 hours open and still reach the 14-16kgf/ grain.5, adopt high-temperature water vapor to handle behind the catalyst extruded moulding, to increase the stability of catalyst.Without the catalyst of steam treatment, its strong acid center is many, and B acid is also higher, and after steam treatment, total acid and B acid all reduce significantly, thereby have increased the stability of catalyst, have reduced carbon deposit.
The performance of the NaZSM-5 molecular screen primary powder that the non-amine method that Nankai University provides is synthetic is as follows:
Sial molecular proportion 38-40
Na
2O% (weight) 2.27
Grain size (μ)-1.0
Degree of crystallinity (%) 85
Adsorptive selectivity % (weight)
N-hexane 5.80
Cyclohexane 1.94
Water 7.90
Embodiment 1 (1) CuCl
2, PdCl
2The preparation of ammonia spirit
Take by weighing 5g PdCl
2Be dissolved in the ammonia spirit of 250ml PH=12, take by weighing the CuCL of 5g equally
2Be dissolved in the ammonia spirit of 250ml PH=12, they be heated to 80 ℃ respectively, till solution was transparent, it was standby to be cooled to room temperature.(2) preparation of HZSM-5 molecular sieve
200g NaZSM-5 type molecular sieve is added 400ml, and concentration is in the hydrochloric acid solution of 0.3N, carries out ion-exchange in temperature is 90-95 ℃ scope, and be 1 hour swap time, carries out repeatedly three times, and filtration washing is to there not being Cl
-, under 110 ℃ of temperature dry 4 hours,, promptly get HZSM-5 type molecular sieve 550 ℃ of roasting temperatures 5 hours.(3) Preparation of catalysts (PdCu/ZSM-5)
100g HZSM-5 molecular sieve is added in the 200ml water, is mixed with slurries, add the PH=12 that ammoniacal liquor is regulated slurries, heat up 90-95 ℃ simultaneously, dropwise add PdCl
2Ammonia spirit and CuCl
2Ammonia spirit, PdCl
2The addition 31.8ml of solution, CuCl
2The addition 30.2ml of solution, mixed liquor stirred 1 hour down at 90-95 ℃, washed, filters, is washed till Cl afterwards
-, drying is 4 hours under 110 ℃ of temperature,
Adding is by 5.1ml nitric acid and 61.1g Al (OH)
3The adhesive that is modulated into, behind the extruded moulding under 110 ℃ of temperature dry 4 hours, handled 8 hours at 550 ℃ high-temperature water vapors, must contain Pd0.19% (weight), the catalyst that contains Cu0.17% (weight), this catalyst called after PdCu/ZSM-5 does not have amine type molecular sieve catalyst.The performance of this catalyst see Table-1 and the table-2.
Table-1 contains the PdCu/ZSM-5 that Pd0.19% (weight) contains Cu0.17% (weight)
The performance of no amine type molecular sieve catalyst
Embodiment 2
| Example | Metal is formed | Appreciation condition | Acetone conversion % | Selectivity MIBK % | MIBK yield % | ||||
| Metal | Content, % | Temperature ℃ | Pressure MPa | During air speed -1 | H 2/ acetone | ||||
| Embodiment-1 | Pd Cu | 0.19 0.17 | 170 | 5 | 4.0 | 200 | 36 | 95.4 | 34.34 |
| 160 | 5 | 2.0 | 200 | 42.21 | 95.36 | 40.25 | |||
With embodiment 1, just at (3) step PdCl
2The addition of solution is 53.7ml, CuCl
2The addition of solution is 69.7ml, and other step is with embodiment 1, make to contain Pd0.32% (weight), and the PdCu/ZSM-5 molecular sieve catalyst of cupric 0.39% (weight), the performance of this catalyst sees Table-2.
Table-2 contains the PdCu/ZSM-5 that Pd0.32% (weight) contains Cu0.39% (weight)
The performance of no amine type molecular sieve catalyst
Reference example-1
| Example | Metal is formed | Appreciation condition | Acetone conversion % | Selectivity MIBK % | MIBK yield % | ||||
| Metal | Content, % | Temperature ℃ | Pressure MPa | During air speed -1 | H 2/ acetone | ||||
| Embodiment-2 | Pd | 0.32 | 170 | 5 | 4.0 | 200 | 38 | 95.3 | 36.21 |
| Cu | 0.39 | ||||||||
Same embodiment-1 just (3) step, does not add CuCl
2Solution, PdCl
2Be incorporated as 79.8ml, must contain the Pd/ZSM-5 molecular sieve catalyst of Pd0.48% (weight).The performance of this catalyst sees Table-3.
Table-3 Pd/ZSM-5 that contain Pd0.48% (weight) do not have the performance of amine type molecular sieve catalyst
| Example | Metal is formed | Appreciation condition | Acetone conversion % | Selectivity MIBK % | MIBK yield % | ||||
| Metal | Content, % | Temperature ℃ | Pressure MPa | During air speed -1 | H 2/ acetone | ||||
| Reference example-1 | Pd | 0.48 | 174 | 5 | 4.0 | 200 | 25.14 | 97.33 | 24.49 |
Claims (13)
1, a kind of catalyst that is used for acetone one-step method synthesize methyl-isobutyl ketone, be carrier wherein with the ZSM-5 molecular sieve, with Metal Palladium (Pd) is active component, it is characterized in that the carrier that is adopted is with the synthetic ZSM-5 molecular sieve of non-amine method, it is auxiliary agent that catalyst adds IB family element, the content of metal Pd is 0.01-0.4% (weight), and the content of IB family metal is 0.01-0.4% (weight), and alumina content is 20-30% (weight).
2, according to the catalyst of claim 1, IB family element is selected copper for use.
3, according to the catalyst of claim 2, the content of Pd is 0.15-O.25% (weight).The content range of Cu is 0.15-0.25% (weight).
4, a kind of method for preparing catalyst that is used for acetone one-step method synthesize methyl-isobutyl ketone, wherein that non-amine method is synthetic ZSM-5 molecular screen primary powder with inorganic acid exchange HZSM-5 type molecular sieve, it is characterized in that HZSM-5 type molecular sieve pulp and PdCl
2And CuCl
2Ammonia spirit mix, carry out ion-exchange, wash then, filter, dry, add Al (OH)
3Behind the adhesive extruded moulding, drying, and high-temperature water vapor handle, promptly make the present invention's catalyst.
5, according to the preparation method of claim 4, prepare PdCl
2And CuCl
2Ammonia spirit, control solution pH=10-12, PdCl
2Concentration is 2% (weight) CuCl
2Concentration 2% (weight), solution is heated to 75-80 ℃, constant temperature is transparent to solution.
6, according to the preparation method of claim 4, HZSM-5 molecular sieve pulp and PdCl
2And CuCl
2Ammonia spirit mixes when carrying out ion-exchange, and the exchange temperature is 90-95 ℃.
7, according to the preparation method of claim 4, the solid-to-liquid ratio of HZSM-5 molecular sieve pulp is 1: 2, adds the PH=10-12 of ammoniacal liquor adjusting slurry.
8, according to the preparation method of claim 4, HZSM-5 molecular sieve pulp and PdCl
2And CuCl
2Ammonia spirit mix, be 1 hour the swap time of carrying out ion-exchange.
9, according to the preparation method of claim 4, HZSM-5 molecular sieve pulp and PdCl
2, CuCl
2Ammonia spirit mixes when carrying out ion-exchange, adds the NH of 1% (weight)
4Cl (calculating with the catalyst butt) is the absorption competition agent.
10, according to the preparation method of claim 4, the Al of adhesive (OH)
3Addition with Al
2O
3The weight meter accounts for the 20-30% of catalyst weight.
11, according to the preparation method of claim 4, during preparation HZSM-5 molecular sieve, the acid of being adopted is inorganic acid, and concentration is 0.2-1.0N.
12, according to the preparation method of claim 11, the inorganic acid that is adopted: be concentration of hydrochloric acid: be 0.2-0.4N.
13, according to the preparation method of claim 4, during preparation HZSM-5 molecular sieve, control exchanges 90-95 ℃ of temperature, and the exchange number of times is three times, and be 1 hour each swap time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91105999A CN1034476C (en) | 1991-08-29 | 1991-08-29 | Synthetic methyl isobutyl acetone molecular sieve catalyst and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91105999A CN1034476C (en) | 1991-08-29 | 1991-08-29 | Synthetic methyl isobutyl acetone molecular sieve catalyst and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069674A CN1069674A (en) | 1993-03-10 |
| CN1034476C true CN1034476C (en) | 1997-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91105999A Expired - Fee Related CN1034476C (en) | 1991-08-29 | 1991-08-29 | Synthetic methyl isobutyl acetone molecular sieve catalyst and its preparation method |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037068C (en) * | 1994-03-12 | 1998-01-21 | 湖北省化学研究所 | Absorptive sweetening agent for room temp. conversion of hydrogen sulfide, carbonyl sulfide, carbon disulfide and preparation thereof |
| CN103420786B (en) * | 2012-05-14 | 2015-12-16 | 浙江新化化工股份有限公司 | The method of coproducing methyl isobutyl ketone and methyl isobutyl carbinol |
| CN103801332B (en) * | 2012-11-08 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of preparation method of vulcanization type palladium/aluminium oxide catalyst |
| CN104588041B (en) * | 2013-11-01 | 2017-02-22 | 中国石油化工股份有限公司大连石油化工研究院 | Palladium/alumina catalyst and preparation method thereof |
| CN105439840A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A one-step method of preparing methyl isobutyl ketone from acetone |
| CN109701549B (en) * | 2017-10-26 | 2022-03-29 | 中国石油化工股份有限公司 | Catalyst for preparing methyl isobutyl ketone by acetone one-step method and preparation method and application thereof |
| CN114534775A (en) * | 2022-02-25 | 2022-05-27 | 厦门大学 | Catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4339606A (en) * | 1981-02-06 | 1982-07-13 | Mobil Oil Corporation | Conversion of ketones over metal-containing zeolite catalysts |
| CN85100463A (en) * | 1985-04-03 | 1986-02-10 | 南开大学 | " direct method " synthesizes the ZSM-5 molecular sieve |
-
1991
- 1991-08-29 CN CN91105999A patent/CN1034476C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4339606A (en) * | 1981-02-06 | 1982-07-13 | Mobil Oil Corporation | Conversion of ketones over metal-containing zeolite catalysts |
| CN85100463A (en) * | 1985-04-03 | 1986-02-10 | 南开大学 | " direct method " synthesizes the ZSM-5 molecular sieve |
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| Publication number | Publication date |
|---|---|
| CN1069674A (en) | 1993-03-10 |
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