CN1289641A - Solid acid catalyst containing heteropoly acid and its preparing process - Google Patents
Solid acid catalyst containing heteropoly acid and its preparing process Download PDFInfo
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- CN1289641A CN1289641A CN 99113280 CN99113280A CN1289641A CN 1289641 A CN1289641 A CN 1289641A CN 99113280 CN99113280 CN 99113280 CN 99113280 A CN99113280 A CN 99113280A CN 1289641 A CN1289641 A CN 1289641A
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Abstract
A heteropolyacid-containing solid acid catalyst for ammoniation reaction, hydration reaction, or ethering reaction of olefine contains heteropoly acid (0.01-10 wt%), zeolite (30-90) and gamma Al2O3 (10-70), and is prepared through mixing zeolite with precussor of gamma-Al2O3, adding aqueous solution of nitric acid and deionized water, shaping, drying, calcining to obtain carrier, immersing carrier in aqueous solution containing hetenopoly acid, drying and calcining. Its advantages are high transform rate and selectivity, long service life, and lower by-product.
Description
The present invention relates to a kind of solid acid catalyst that contains heteropoly acid and preparation method thereof.
Heteropoly acid has a wide range of applications in petrochemical industry and organic synthesis as a kind of effective catalyst that has acid and OR performance concurrently.
United States Patent (USP) 4175210 in 1979, and people's applying silicon wolframic acids such as Selwitz are synthetic in the ethers gas phase, and catalyst is with SiO
2SiO for carrier
212WO
3Be adapted to the etherificate of various alkene or alkene mixture and 1-3 carbon alcohol or alcohol mixture.HPA content 30%～100% in the catalyst, gas phase, liquid hourly space velocity (LHSV) 0.1～0.5h
-1, 80～120 ℃ of reaction temperatures, pressure 0.01～1MPa or higher.Alfin mol ratio 2～5: 1.Method for preparing catalyst is: Fisher scientific commodity silico-tungstic acid is soluble in water that 422.9g contains 21.82%SiO
2-12WO
3Solution.Carrier is 215.3g Davison70 silica gel (the 10-20 order is at 1000 following roasting 10h).Carrier with obtain net weight 638.2g solid after heteropoly acid mixes, at 120 ℃ of dry down 310g dry products.At 400 ℃ of following roasting 16h, obtain containing the catalyst of 30% heteropoly acid again.Mostly be 5～8 carbon olefins and methanol etherification during institute gives an actual example, do not comprise propylene.
One nine eight zero year petrochemical industries the 9th phase document is that catalyst carries out alkene direct hydration preparing isopropanol with the heteropoly acid (mainly being silico-tungstic acid) and the soluble salts aqueous solution thereof.Catalyst concn is 1 * 10 in the aqueous solution
-3Gmol/l, 230 ℃ of reaction temperatures, when reaction pressure 20.0MPa, IPA yield 200g alcohol/catalyst, HPA selectivity 98%.The propylene conversion per pass is up to 65%～70%, and catalyst life is long, can recycle repeatedly.Shortcoming is the reaction pressure height.
In 1994 Chem Res, Chin, University the tenth interim Zhao is originally bright to wait the people to study methyl alcohol and propylene oxide etherificate.Think that the HPA of Dawson structure is arranged is better than what the Keggin structure was arranged.Heteroplyblue is best among the HPA.The general poor activity of heteropoly acid salt shows the acidity (acidity) of catalyst activity from catalyst.This technical process is to utilize the excessive generation with the polymerisation of drawing up of methyl alcohol, but the olefinic polymerization of part is still arranged, so selectivity is on the low side.
The purpose of this invention is to provide a kind of solid acid catalyst that contains heteropoly acid and preparation method thereof, this catalyst is applied to alkene aminating reaction, olefin hydration reaction and etherification reaction etc. and shows higher conversion ratio and selectivity, can reduce raw material consumption, energy consumption and product cost.
With the percentage by weight is benchmark, and catalyst of the present invention contains:
1) zeolite 30%～90%, and preferably 50%～70%, zeolite can be one or more in USY, REUSY, H β, NTY, SSY, ZSM, the modenite, described SiO
2/ Al
2O
3Mol ratio is 20～100.
2) heteropoly acid content 0.01%～10%, is preferably 0.5%～6%, and heteropoly acid can be HsO
4, H
3PO
4, 20MoO
32H
3PO
448H
2O, H
2[P (W
2O
7)
5.5(Mo
2O
3)
0.5], H
4[Si (W
3O
10)
4], 20WO
32H
3PO
425H
2O, H
4S[Si (W
3O
14)
4] and its esters such as Cu
1.5HS[Si (W
3O
14)
4], AlHS[Si (W
3O
14)
4], Zn
1.5HS[Si (W
3O
14)
4], Na
3HS[Si (W
3O
14)
4], FeHS[Si (W
3O
14)
4] etc., be preferably silico-tungstic acid or phosphotungstic acid.
3) γ-Al
2O
310%～70%, be preferably 30%～50%.
This Preparation of catalysts method is as follows:
(1) with zeolite and γ-Al
2O
3Precursor mix pinch, moulding, dry; Detailed process can for: with zeolite and γ-Al
2O
3Precursor mix, add entry and aqueous solution of nitric acid (concentration is preferably 10%～20%) or phosphate aqueous solution (concentration is preferably 10%～15%), mix then pinch, moulding, dry; (preferably adopting deionized water and concentration is 10%～15% aqueous solution of nitric acid); Nitric acid or phosphoric acid addition can be according to nitric acid or phosphoric acid and γ-Al
2O
3Mol ratio is 0.1～0.5: 1 adding, is preferably 0.2～0.3: 1; The addition of water is pinched mixing, moulding is as the criterion;
(2) the shaping thing drying that obtains of step (1) can be under 100～170 ℃ condition dry 4～16 hours;
The shaping thing of (3) roasting drying, can be under 400～700 ℃ of conditions roasting 5～12 hours, make the carrier of catalyst of the present invention;
(4) after the carrier that step (3) is made flooded with the aqueous solution that contains heteropoly acid, drying was 8～12 hours under 100～150 ℃, and then 500～600 ℃ of following roastings 4～8 hours, promptly gets catalyst of the present invention.
Catalyst of the present invention can be used for the alkene aminating reaction and produces the reaction of aminate, olefin hydration and produce alcohol, etherification reaction and produce the process that ether is produced in ether and olefin hydration reaction.For example, can be used for propylene hydration and prepare that isopropyl alcohol, propylene hydration prepare diisopropyl ether, the direct ammonification of isobutene prepares tert-butylamine and isobutene and methanol etherification and prepares the MTBE reaction.In addition, the present invention also can be used for replacing sulfuric acid to be applied to various acid catalyzed reactions.
According to the prepared catalyst of the present invention, can directly use.
Compared with prior art, the present invention has following advantage and effect:
Because catalyst of the present invention contains heteropoly acid, zeolite, compare with other acid catalysts such as amorphous silicon aluminium, aluminium oxide and the zeolite catalyst that do not contain heteropoly acid, can avoid equipment corrosion, improve operating environment, and conversion ratio is significantly improved, selectivity of product also increases, and the by-product rate decreases.
Embodiment 1
Get 30gREUSY zeolite (SiO
2/ Al
2O
3=50 mix with the 36gSB powder, add 15% phosphoric acid,diluted 54g, mix on banded extruder and pinch the back extruded moulding, making diameter is the catalyst bar of 1.5mm, then 120 ℃ of dryings 12 hours, again in muffle furnace in 550 ℃ of roastings 6 hours, then with 5% silicon tungsten acid solution 40g dipping, 100 ℃ dry 10 hours down, then 600 ℃ of following roastings 4 hours, promptly get catalyst A of the present invention, its heteropoly acid content 3% (w), γ-Al
2O
3Content 43% (w), zeolite content 54% (w).
Embodiment 2
Get 30gH β zeolite (SiO
2/ Al
2O
3=60.2) mix with the above-mentioned SB powder of 20g, add 14% aqueous solution of nitric acid 30g, on banded extruder, mix and pinch the back extruded moulding, making diameter is the catalyst bar of 1.5mm, then 120 ℃ of dryings 12 hours, again in muffle furnace in 550 ℃ of roastings 6 hours, aqueous solution 30g with 5% phosphotungstic acid floods then, drying is 10 hours under 120 ℃, then 550 ℃ of following roastings 8 hours, promptly get catalyst B of the present invention, its heteropoly acid content 3% (w), γ-Al2O3 content 30% (w), zeolite content 67% (w).
Embodiment 3～4
Making silico-tungstic acid content according to embodiment 1 described method is 1% (w), 5% (w); γ-Al
2O
3Content is 40% (w), 35% (w); Zeolite content is catalyst C, the D of 59% (w), 60% (w).
Comparative example 1
According to the method for embodiment 1, just do not add heteropoly acid, make γ-Al
2O
3Content 60% (w); The catalyst E of REUSY zeolite content 40% (w).
Comparative example 2
According to the method for embodiment 2, just do not add heteropoly acid, make γ-Al
2O
3Content 40%; The catalyst F of H β content 60%.
Embodiment 5～8
Catalyst breakage among the embodiment 1～4 is become 8～20 orders, respectively get 20g and be respectively charged into internal diameter 12mm, in the stainless steel reactor of long 650mm, isobutene and ammonia add reactor top with measuring pump, and inlet amount is that (weight space velocity is 1.0h to 33ml/h
-1), ammonia/alkene mol ratio is 2.0,280 ℃ of reaction temperatures, reaction pressure 8.0MPa, reaction mass flows out from reactor bottom puts into the normal pressure separator through cooling, unreacted alkene and ammonia are discharged from separator top, and bottom liquid phases is weighed and calculated conversion ratio and with the gas chromatographic analysis composition, it the results are shown in following table 1.
Comparative example 3～6
According to the process of embodiment 5～8, just catalyst adopts E, F, unformed SiO respectively
2-Al
2O
3(Al
2O
3Content 25% (w)) and γ-Al
2O
3, other is with embodiment 5～8, and it the results are shown in table 1.
Table 1
| Embodiment or comparative example | Catalyst | Isobutene conversion per pass % | Amine selectivity % | ||
| Numbering | Silica alumina ratio | Heteropoly acid content (%) | |||
| Embodiment 5 | ????A | ????50 | ????3．0 | ????11．5 | ????97 |
| Embodiment 6 | ????B | ????60．2 | ????3．0 | ????12．0 | ????96 |
| Embodiment 7 | ????C | ????50 | ????1．0 | ?????9．5 | ????95 |
| Embodiment 8 | ????D | ????50 | ????5．0 | ????10．0 | ????93 |
| Comparative example 3 | ????E | ????50 | Do not have | ?????5．4 | ????96 |
| Comparative example 4 | ????F | ????60．2 | Do not have | ?????6．2 | ????97 |
| Comparative example 5 | Unformed SiO 2-Al 2O 3 | ?????3．1 | ????93 | ||
| Comparative example 6 | ????γ-Al 2O 3 | ?????2．3 | ????90 | ||
Find out that from the data of table 1 catalyst of the present invention significantly is better than not containing the zeolite-γ-Al of heteropoly acid
2O
3, unformed SiO
2-Al
2O
3And γ-Al
2O
3
Embodiment 9～12, comparative example 7～8
Catalyst breakage in embodiment 1～4, the comparative example 1～2 is become 8～20 orders, respectively get 50ml and be respectively charged into internal diameter 12mm, in the stainless steel reactor of long 650mm, propylene and water add reactor with measuring pump, and the propylene feed volume space velocity is 0.3h
-1, water/alkene mol ratio is 13.6: 1,240 ℃ of reaction temperatures, reaction pressure 10.0MPa flows out reaction mass from reactor and puts into the normal pressure separator through cooling, and unreacted alkene is discharged from the separator top, bottom liquid phases is formed with gas chromatographic analysis, and it the results are shown in following table 2.
Table 2
| Embodiment or comparative example | Catalyst | Propylene conversion % | Isopropyl alcohol selectivity % | ||
| Numbering | Silica alumina ratio | Heteropoly acid content (%) | |||
| Embodiment 9 | ????A | ????50 | ????3．0 | ????35．5 | ????95．5 |
| Embodiment 10 | ????B | ????60．2 | ????3．0 | ????27．3 | ????93 |
| Embodiment 11 | ????C | ????50 | ????1．0 | ????35．5 | ????97 |
| Embodiment 12 | ????D | ????50 | ????5．0 | ????40．5 | ????90 |
| Comparative example 7 | ????E | ????50 | Do not have | ????11．8 | ????92 |
| Comparative example 8 | ????F | ????60．2 | Do not have | ????8．9 | ????93 |
Embodiment 13～16, comparative example 9～10
Catalyst breakage in embodiment 1～4, the comparative example 1～2 is become 8～20 orders, respectively get 50ml and be respectively charged into internal diameter 12mm, in the stainless steel reactor of long 650mm, propylene and water add reactor with measuring pump, and the propylene feed volume space velocity is 0.5h
-1, water/alkene mol ratio is 1.0,155 ℃ of reaction temperatures, reaction pressure 8.0MPa flows out reaction mass from reactor and puts into the normal pressure separator through cooling, and unreacted alkene is discharged from the separator top, bottom liquid phases is formed with gas chromatographic analysis, and it the results are shown in following table 3.
Table 3
| Embodiment | Catalyst | Propylene conversion per pass % | Diisopropyl ether selectivity % | ||
| Numbering | Silica alumina ratio | Heteropoly acid content (%) | |||
| ????13 | ????A | ????50 | ????3．0 | ????35．4 | ????40 |
| ????14 | ????B | ????60．2 | ????3．0 | ????28．5 | ????45 |
| ????15 | ????C | ????50 | ????1．0 | ????25．5 | ????56 |
| ????16 | ????D | ????50 | ????5．0 | ????54．0 | ????36 |
| Comparative example 9 | ????E | ????50 | Do not have | ????18．0 | ????39 |
| Comparative example 10 | ????F | ????60．2 | Do not have | ????20．5 | ????35．5 |
Embodiment 17～20, comparative example 11～12 become 8～20 orders with the catalyst breakage in embodiment 1～4, the comparative example 1～2, respectively get 50ml and be respectively charged into internal diameter 12mm, in the stainless steel reactor of long 650mm, isobutene and methyl alcohol add reactor with measuring pump, and the isobutylene feed volume space velocity is 1.5h
-1, 100 ℃ of reaction temperatures, reaction pressure 1.25MPa, alcohol/alkene (mol) is 1.2: 1.Flow out reaction mass from reactor and put into the normal pressure separator through cooling, unreacted alkene is discharged from the separator top, and bottom liquid phases is formed with gas chromatographic analysis, and it the results are shown in following table 4.
Table 4
| Embodiment | Catalyst | Isobutene conversion % | MTBE selectivity % | ||
| Numbering | Silica alumina ratio | Heteropoly acid content (%) | |||
| Embodiment 17 | ????A | ????50 | ????3．0 | ????90．5 | ????99 |
| Embodiment 18 | ????B | ????60．2 | ????3．0 | ????92．5 | ????98 |
| Embodiment 19 | ????C | ????50 | ????1．0 | ????90 | ????100 |
| Embodiment 20 | ????D | ????50 | ????5．0 | ????95 | ????95 |
| Comparative example 11 | ????E | ????50 | Do not have | ????56 | ????97 |
| Comparative example 12 | ????F | ????60．2 | Do not have | ????65 | ????96．5 |
Claims (15)
1, a kind of solid acid catalyst that contains heteropoly acid is a benchmark with the percentage by weight, comprising:
1) zeolite 30%～90%;
2) heteropoly acid content 0.01%～10%;
3) γ-Al of 10%～70%
2O
3
2, according to the described solid acid catalyst that contains heteropoly acid of claim 1, it is characterized in that described zeolite SiO
2/ Al
2O
3Molecular proportion is 20～100.
3,, it is characterized in that described heteropoly acid is HsO according to the described solid acid catalyst that contains heteropoly acid of claim 1
4, H
3PO
4, 20MoO
32H
3PO
448H
2O, H
2[P (W
2O
7)
5.5(Mo
2O
3)
0.5], H
4[Si (W
3O
10)
4], 20WO
32H
3PO
425H
2O, H
4S[Si (W
3O
14)
4] and corresponding salt in one or more.
4,, it is characterized in that described zeolite content is that benchmark is 50%～70% with the percentage by weight of catalyst according to the described solid acid catalyst that contains heteropoly acid of claim 1.
5, according to the described solid acid catalyst that contains heteropoly acid of claim 1, it is characterized in that described heteropoly acid content is benchmark with the percentage by weight of catalyst, be 0.5%～6%.
6, according to the described solid acid catalyst that contains heteropoly acid of claim 1, it is characterized in that described γ-Al
2O
3Content is benchmark with the percentage by weight of catalyst, is 30%～50%.
7,, it is characterized in that described heteropoly acid is a silico-tungstic acid according to the described solid acid catalyst that contains heteropoly acid of claim 1.
8,, it is characterized in that described heteropoly acid is a phosphotungstic acid according to the described solid acid catalyst that contains heteropoly acid of claim 1.
9,, it is characterized in that described zeolite is one or both among REUSY, the H β according to the described solid acid catalyst that contains heteropoly acid of claim 1.
10,, it is characterized in that described corresponding salt is Cu according to the described solid acid catalyst that contains heteropoly acid of claim 1
1.5Hs[Si (W
3O
14)
4], AIHS[Si (W
3O
14)
4], Zn
1.5HS[Si (W
3O
14)
4], Na
3HS[Si (W
3O
14)
4], FeHS[Si (WO
3O
14)
4] in one or more.
10, a kind of preparation method who contains the solid acid catalyst of heteropoly acid comprises:
1) with zeolite and γ-Al
2O
3Precursor, water and nitric acid or phosphoric acid mix pinch, moulding, airing;
2) the shaping thing that step 1) is made was 100～170 ℃ of dryings 4～16 hours;
3) Gan Zao shaping thing roasting 5～12 hours under 400～700 ℃ of conditions makes catalyst carrier;
4) carrier that step 3) made is with the aqueous solution dipping that contains heteropoly acid, drying, roasting then, makes catalyst.
11, the application of the described solid acid catalyst of a kind of claim 1 is characterized in that described catalyst is used for the process that the alkene aminating reaction is produced aminate.
12, the application of the described solid acid catalyst of a kind of claim 1 is characterized in that described catalyst is used for the process that alcohol is produced in the olefin hydration reaction.
13, the application of the described solid acid catalyst of a kind of claim 1 is characterized in that described catalyst is used for the process that etherification reaction is produced ether.
14, the application of the described solid acid catalyst of a kind of claim 1 is characterized in that described catalyst is used for the process that ether is produced in the olefin hydration reaction.
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|---|---|---|---|
| CN99113280A CN1101265C (en) | 1999-09-29 | 1999-09-29 | Solid acid catalyst containing heteropoly acid and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113280A CN1101265C (en) | 1999-09-29 | 1999-09-29 | Solid acid catalyst containing heteropoly acid and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1289641A true CN1289641A (en) | 2001-04-04 |
| CN1101265C CN1101265C (en) | 2003-02-12 |
Family
ID=5276487
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|---|---|---|---|
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1999
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