CN1274418C - Phosphorous-aluminium-mixed oxide catalyst, process for its preparation and use thereof - Google Patents
Phosphorous-aluminium-mixed oxide catalyst, process for its preparation and use thereof Download PDFInfo
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- CN1274418C CN1274418C CNB200410070562XA CN200410070562A CN1274418C CN 1274418 C CN1274418 C CN 1274418C CN B200410070562X A CNB200410070562X A CN B200410070562XA CN 200410070562 A CN200410070562 A CN 200410070562A CN 1274418 C CN1274418 C CN 1274418C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title claims description 18
- 230000008569 process Effects 0.000 title description 3
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 26
- -1 benzenes monoalky lether Chemical class 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 abstract 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
An A1 and P mixed oxide, with surface area 50-100 m<2>/g, prepared by gradually heating up to 400-800 DEG C a mixed compound in its turn obtained by coprecipitation from an aqueous solution of A1 and P compounds, is advantageously used as a catalyst for the monoalkylation of diphenol compounds.
Description
Technical field
The present invention relates to phosphorous-aluminium-mixed oxide catalyst, its preparation method and its usage, particularly a kind of method that is used to prepare the polyhydroxy benzenes monoalky lether.
Background technology
Diphenol monoalkyl ethers such as o-methoxyphenol (1-methoxyl group-2-hydroxy benzenes) and o-ethoxyphenol (guetol, 1-ethyoxyl-2-hydroxy benzenes) and other diphenol monoalkyl ethers, can prepare by the condensation reaction (etherificate) of catechol or other diphenols and alkylating agent, use a kind of suitable this transformation of material catalysis simultaneously, this suitable material has the advantages that to promote monoalkylation formation monoalky lether at the oxygen atom place.This reaction is carried out in can or mixing mutually in gas phase, liquid phase, and preferred alkylating agent is corresponding alcohol.
Disclosed catalyst system and catalyzing is based on the system of boron and phosphorus mixed oxide in patent documentation, as with described in the EP 420 756 (1990) of the name application of UBE Industries.This material is characterized in that significant catalytic activity, yet this catalytic activity is along with reduce time lapse gradually, because activity slowly but little by little reduces mutually under reaction condition.For fear of this problem, the volatile compound of B and/or P is feed simultaneously, in case active component is lost by sublimation under reaction condition.Alternatively, active reduction can be avoided by increasing reaction temperature, yet, increase reaction temperature and cause desired product selectivity decline.In addition, the peptizaiton gradually of active phase has reduced the mechanical strength of catalyst extrudate or pellet.
On the other hand, FR 2,303,784 (with the name application of UBE Industries, 1976) disclose purposes based on the catalyst system and catalyzing of Al/B/P/O, this catalysis system still requires to supply with the compound of B and/or P, so that the performance that keeps relevant reagent to transform does not pass in time and changes.
At last, EP 509,927 (with the name application of UBE Industries, 1992) discloses a kind of by Al
aP
bTi
cSi
dO
eThe purposes of the catalyst that mixed oxide is formed, in this mixed oxide, the atomic ratio of said components is (when a=1), b=1.0-1.6, C=0.05-0.5, d=0.05-0.2.A kind of alkali metal ion (normally potassium) can also be added in the composition and (press the 0-0.9 ratio).Compare with the catalyst system and catalyzing that has earlier, this individual system has some advantages and is: its reactive characteristics are much more constant along with time lapse, and therefore do not need to make each volatile compound feed simultaneously.Above-mentioned catalyst is characterized in that: in temperature range is 300-600 ℃, preferably under 400 ℃, carries out after the last heat treatment, and specific area is at 30-50m
2In the scope of/g.It is etherification reaction under 200-400 ℃ that this catalyst is used for described temperature range.Should emphasize, according to above-mentioned patent, be provided with Ti or Si in catalyst is formed, this causes the selectivity to o-methoxyphenol (etherificate that is used for catechol and methyl alcohol) to reduce, and especially, causes catalytic activity significantly to reduce.In fact, under 280 ℃ of temperature, conversion ratio reduces, and from 64.7% to 46.3% (catalyst that does not have Ti) is to 55.7% (catalyst that does not have Si); Selectivity reduces, and from 98.3% to 95.8% (catalyst that does not have Ti) is to 97.4% (catalyst that does not have Si).
In view of the foregoing, very be desirable to provide a kind of catalyst, its specific activity is above-mentioned or known catalysts is bigger, so that operate under the reaction condition of milder, from then on provides the qualified conversion ratio that monoether class (for example o-methoxyphenol) is had high selectivity.A desirable system should be to operate under than the lower reaction temperature of the reaction temperature described in the patent documentation, that is the formation of undesired product is reduced under the minimum condition operate.
The present invention relates to a kind of catalyst system and catalyzing based on Al/P/O, this catalyst system and catalyzing according to the preparation of technology different described in the patent documentation, and this catalyst system and catalyzing compares with the prior art system, has the following advantages:
1) specific area height is calcined (roasting) afterwards down at 400-800 ℃ (preferably 400-650 ℃), at 40-100m
2In/g the scope because used preparation method, so this specific area be significantly higher than described in the document and under uniform temp the specific area of the system after the calcining.
2) because the 1st) characteristics of point, solid can be higher than under the temperature described in the document, for example stands thermal sintering and handle under 600 ℃, and keep high specific area simultaneously, at 50-80m
2In/g the scope, and therefore keep high catalytic activity.Under higher temperature, handle the material that is characterized in higher structure and morphological stability is provided, cause catalytic performance to be passed in time and more stable.
3) because the 1st) and the 2nd) characteristics put, even when not having Si and Ti component to exist, also can obtain the catalyst system and catalyzing activity.As a result, can the lower catalyst of preparation cost with simpler method, these methods have better reappearance, wherein preparation property with the remarkable step-down of composition parameter.
4) can work being lower than under the temperature described in the document with the catalyst of method of the present invention preparation, and therefore aspect desired product selectivity and catalyst itself service life two, more working under the advantageous conditions.In fact, the phosphatic hydrolysis that lower temperature delay always exists reduces the heavy product that produces passivation (deactivation) problem simultaneously and forms.For example, under 190 ℃ of temperature, can obtain the catechol conversion ratio is 20-30%, and reaction surpasses 1,300 hour to flow process simultaneously, and the selectivity of o-methoxyphenol surpasses 99%, and does not reduce reactive.Unconverted reagent can be easy to be recycled in the reaction medium then.
Summary of the invention
The present invention relates to a kind of catalyst, this catalyst is used for by reaction between polyhydroxy benzenes compounds and the alcohol polyhydroxy benzenes being carried out oxygen monoalkylation (monoetherization), more particularly, is used for dihydroxy benzenes class and straight or branched, saturated or unsaturated, C
1-C
6, preferred C
1-C
4Reaction between the alcohols.Reaction can be in gas phase, or in mixing mutually, carry out, the high conversion that has the reagent of qualification simultaneously, with to oxygen monoalkylated product (1-alkoxyl-2-hydroxy benzenes, 1-methoxyl group-2-hydroxy benzenes or o-methoxyphenol for example) has high selectivity, and, have low selectivity such as the complete product (for example o-dimethoxybenzene) of etherificate to other undesired products.Another advantage of catalyst of the present invention is: reaction can be carried out very time long-life and not make catalyst passivation aspect active and selectivity; There is no need to allow compound with reagent while feed, constant with the performance of catalyst after keeping after a while itself.Usually, known in the literature catalyst system, under system situation based on boron, phosphorus and oxygen, must be with all cpds such as alkyl borate, alkylphosphonic or other volatile boron and phosphorus compound while feed; Wherein along with the B/P/O mixing cpd in reaction medium lentamente but hydrolysis continuously, catalyst loses activity gradually, and boron and phosphorus discharge with the volatile compound form.Form vapour pressure by supplying with B and P-compound continuously, prevent or delay passivating process at least.Yet the continuous feeding of above-claimed cpd causes this method at reagent cost and make above-claimed cpd and unconverted reagent and the added burden aspect the product separate operation.In addition, B and/or P-compound be the possibility hydrolysis in the presence of water vapour, so the existence of B and/or P-compound can cause undesirable corrosiveness in the downstream of reactor itself.
Catalyst of the present invention can be worked there not being addition compound to send into continuously under the situation of reactor, and does not observe the reduction of catalytic activity and general performance (in the yield aspects of the selectivity and the product of wanting) at least between 1,300 hour stage of reaction.The most important advantage of catalyst system of the present invention is: work under its can be in being lower than document used temperature; In fact caltalyst of the present invention ties up under 170-200 ℃ the temperature range, advantage be under 190 ℃ of temperature, to work effectively, this temperature is outside the temperature range described in the EP 509,927 for example.
Catalyst of the present invention is made up of aluminium oxide and phosphorous oxides, and they exist with aluminium and phosphorus mixed oxide Al/P/O form, and wherein the atomic ratio of aluminium/phosphorus is in the 0.40-1.0 scope, preferably in the 0.60-0.80 scope.Opposite with the explanation based on phosphatic material of other patent disclosure, the present invention does not have other admixture component to be added to increases the stable and active of catalyst itself in the catalyst composition.
The preparation of catalyst material of the present invention is to make the compound co-precipitation of Al and P, obtains the precursor of final catalyst.Generally, preparation is to begin to carry out with water soluble aluminum compound and water-soluble phosphorus compound.With this two kinds of compounds dissolving, make each element co-precipitation by changing pH value of solution then, thereby obtain a kind of precursor, then precursor is filtered, dry and at high temperature in air, handle at last.Following method provides as the example that is used to prepare catalyst method of the present invention, and does not plan to limit the scope of the invention.For preparation under condition of the present invention has catalyst to the useful characteristics of monoether reaction, the most important condition that is used to prepare the suitable product parent is: i) prepare a kind of homogeneous solution; Ii) pass through suitably regulator solution pH, make Al and P with the co-precipitation of oxygenated water compound (oxohydrates) form.Therefore, the Al that satisfies above-mentioned condition of any kind and P soluble compound may be used to purpose of the present invention.
Six hydration alchlors and 85% orthophosphoric acid are water-soluble; Especially, the Al compound is dissolved in the HCl acidic aqueous solution, solution is remained on roughly under the room temperature (avoid compound hydrolysis and therefore avoid aluminum hydroxide precipitation).Above-mentioned solution and phosphoric acid are added together, and be about 7 to pH, keep this pH value then, make the mixing cpd co-precipitation by the hydro-oxidation ammonium.Alternatively, the solution that contains Al and P dropwise can be joined a kind of pH and be in (for example containing ammonium acetate) solution of 7, keep this pH value by ammonification or other alkali compounds simultaneously.
Sediment general (but be not must) is gel form, and sediment is preferably at 80-180 ℃, more preferably 100-150 ℃ of drying and calcine some hrs (alternatively, coprecipitate can directly be calcined) at last in air down.Calcining is under 400-800 ℃ in temperature range, preferably under 400-650 ℃, and most preferably carries out according to following timetable:
-be heated to 280-320 ℃ with about 10 ℃/minute speed from room temperature;
-stopped 3-5 hour down at 280-320 ℃;
-further be heated to 580-620 ℃ with about 10 ℃/minute speed.
-stopped 3-5 hour down at 580-620 ℃.
The catalyst net shape can be any shape that is adapted at using in the fixed bed reactors, as extrudate, pellet or the shot-like particle of preparation according to known technique.
Above-mentioned steps is a heat treated example, but these conditions do not limit the present invention in any way.Between each temperature, can suitably change and add thermal gradient and isothermal time, so that optimize heat treatment according to the amount of the catalyst of preparation.
Heat treatment must promote the removal of volatile compound according to known industrial practice.It is mandatory that this is that preparation has a catalyst institute of high surface characteristic.
Alternatively be, can use ammonium hydroxide (or gaseous ammonia), have C
1-C
4The primary amine of alkyl, secondary amine or tertiary amine, their hydroxide is perhaps also used four-(C
1-C
4) alkyl ammonium hydroxide, as precipitating reagent.
This method provides to be had specific area and is higher than 50m
2The solid of/g.
Main difference between the various preparations described in the document is conspicuous in diverse ways.Disclosed catalyst is by with aluminium hydroxide Al (OH) in EP 509,927
3Be dispersed in the water, and (100 ℃ of temperature) this suspension that under agitation refluxes prepares.TiO 2 sol and silicon dioxide gel with appropriate amount adds suspension then, so that reach desirable atomic ratio and add 85% phosphoric acid at last.The suspension that finally forms is stirred and the heating some hrs, and with resulting pastel drying, compression molding with under 400 ℃ of temperature, in air, calcine at last.Like this, the method comprises does not have consoluet Al reagent, and so and final compound is influenced by the primitive character of used aluminium hydroxide.The surface area of above-mentioned patent disclosure after 400 ℃ are handled down, is at 30-50m
2In the scope of/g, it is lower than according to the resulting surface area of the inventive method.
In catalyst of the present invention, especially in the final compound after heat treatment, the Al/P atomic ratio is in the 0.5-1.0 scope, preferably in the 0.6-0.8 scope.Lower or higher ratio all makes catalyst performance, mainly is to desired product selectivity variation.Different ratios also causes significantly reduce service life, refers to that catalytic action keeps the sufficiently stable time between twice regeneration in succession this service life.This is because the peptizaiton of catalyst granules (extrudate or pellet) and because due to carbon product or pitch precipitates on the surface of catalyst itself.
Under catalyst situation of the present invention,, can carry out heat regeneration and handle when being deposited on owing to carbon product or pitch when on the catalyst passivation taking place.It can be under 450-650 ℃ of temperature that typical regeneration is handled, and is more easily under 650 ℃ of temperature, carries out in air stream.Under this temperature, cause the product of passivation and can be removed fully, and lower temperature can not provide this removal completely.Therefore another advantage of system of the present invention is when needs, just can be used to calcine under the temperature identical with the temperature of sintered catalyst itself, effectively regenerate.Advantage is that this regeneration is handled and can not caused and the fresh catalyst change on the ratio characteristic mutually.
By diphenols or generally be the reactivity of the prepared catalyst of the etherificate of polyhydroxy benzenes, with the laboratory flow reactor analysis that the shape catalyst of wanting is housed.Particularly, these reagent (diphenols and alcohol) can be chosen in the evaporimeter after the evaporation, can be together or send into reactor respectively.Can use a kind of carrier gas, preferably nitrogen is transported to each reagent on the catalyst bed of inside reactor.Reactor can be used stainless steel, glass or quartzy the manufacturing.Utilize a suitable heating system that the temperature of catalytic bed is remained under the desired horizontal.Reaction temperature can be in 170-220 ℃ of scope, is to remain in the 180-200 ℃ of scope more easily.
Reagent can be: i) about polyhydroxy benzenes, catechol, hydroquinones or resorcinol (diphenols), also be 1,2-, 1,3-and 1,4-dihydroxy benzenes, perhaps these reagent can have substituent such as methyl or halogen atom on ring, ii) about alcohols, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol and other carbon numbers alcohols up to 6, these alcohols may optionally be undersaturated condition.
Test is the 7.5ml catalyst of packing in the microreactor of laboratory, sends into the liquid mixture that contains 50% weight catechol and 50% methyl alcohol with 3g/h, and carries out under the specific gas flow rate of 35Nml/min.Reaction temperature changes between 190-200 ℃ (example) and 275 ℃ (reference examples).
Example
Example 1
Get the AlCl of 59.2g
36H
2O is along with stirring 200ml 0.5N HCl (190ml H
2O+10ml 37% HCl).Add 21ml 85% weight H subsequently
3PO
4Use dense NH then
4OH (about 90ml) dropwise adds still limpid solution, to regulate pH to about 7.On a filter, formed precipitation is become dry subsequently, so that obtain a kind of pastel by suction.Then pastel is placed in the static drying machine, drying is 12 hours under 120 ℃, so that the whiteness that obtains doing, then whiteness is at high temperature handled in air stream, and adopt following timetable: the heating rate with 10 ℃/min is raised to 300 ℃ from room temperature, 300 ℃ of down insulations 4 hours, then be heated to 600 ℃ from 300 ℃, 600 ℃ of insulations 4 hours down with the heating rate of 10 ℃/min.The surface area of final sample is 74 ± 5m
2/ g.Make then solid through by compression, granulation and screening so that obtain having the shot-like particle of average grain diameter in the 0.5-1mm scope.In final catalyst, the Al/P that measures with plasma spectroscopy analyzes than being 0.64 ± 0.04.
Example 2
Follow with example 1 in identical step, but AlCl
36H
2O and H
3PO
4Amount be respectively 20g and 8.1ml.After heat treatment, Al/P in final catalyst analyzes than being 0.67 ± 0.04.
Reference examples 3
Follow with example 1 in identical step, but AlCl
36H
2O and H
3PO
4Amount be respectively 90.0g and 21.0ml.After heat treatment, the Al/P ratio in final catalyst is 0.95 ± 0.04.
Example 4
Under above-mentioned reaction condition, will in the monoether reaction of catechol and methyl alcohol, test as prepared catalyst as described in the example 1.Particularly, reaction temperature is 190 ℃.Resulting result of the test in the life period of reaction in whole 1300 hours gathers and lists in the table.
Example 5
Catalytic test is under the reaction condition identical with example 4, except reaction temperature is 200 ℃, carries out on the catalyst that makes described in example 1.
Reference examples 6
Catalytic test is under the reaction condition identical with example 4, except reaction temperature is 275 ℃, carries out on the catalyst that makes described in example 1.
Reference examples 7
Catalytic test is under the reaction condition identical with example 4, except reaction temperature is 275 ℃, carries out on the catalyst that makes described in example 2.
Reference examples 8
Catalytic test is under the reaction condition identical with example 4, except reaction temperature is 275 ℃, carries out on the catalyst that makes described in example 3.
Table
Catalytic reaction test in the catechol monoalkylation
| Example/catalyst | T，℃ | *Reaction time hour | The catechol conversion ratio, % | To the selectivity of o-methoxyphenol, % |
| 4/1 | 190 | 156 | 24.9 | 99.2 |
| 4/1 | 190 | 264 | 23.6 | 99.2 |
| 4/1 | 190 | 314 | 23.2 | 99.2 |
| 4/1 | 190 | 863 | 24.1 | 99.1 |
| 4/1 | 190 | 1300 | 23.0 | 99.1 |
| 5/1 | 200 | 600 | 30.0 | 98.7 |
| 6/1 | 275 | 2 | 42.0 | 96.5 |
| 7/2 | 275 | 2 | 51.6 | 95.3 |
| 8/3 | 275 | 2 | 51.5 | 89.3 |
*Reaction time is meant from catalytic test and begins elapsed time.
Example 9
Follow with example 5 in identical step, replace methyl alcohol to make etherifying agent with ethanol simultaneously.Result of the test at 600 hours catalytic life time durations is:
Catechol conversion ratio: 24%
Selectivity to o-ethoxyphenol (guetol): 96%
From top indicated test, can prove:
1) catalyst described in the example 1 kept its reactive characteristics at least 1300 hours, and conversion ratio is higher than 20% and be 99.1%-99.2% (reactive example 4) to the selectivity of o-methoxyphenol simultaneously.
2) catalyst shows described in the example 1, and when testing under surpassing 200 ℃ temperature, loss is to the selectivity of o-methoxyphenol; More particularly, (also once reporting in EP 509,927 examples) under 275 ℃ of temperature, selectivity drops to 96.54% (reactive reference examples 6).
3) catalyst described in the example 2, be prepared into have with example 1 in slightly different atomic ratio, be presented under the identical experiment condition, have similar performance (reactive example 7) with catalyst described in the example 1.
4) catalyst described in the reference examples 3, the Al/P ratio that it is characterized in that catalyst in Al/P ratio and example 1 and 2 is significantly different, it has the catalytic performance than the remarkable variation of catalyst of the present invention, mainly is in variation aspect the selectivity of o-methoxyphenol (reactive reference examples 8).
Example 10
Follow the step of example 4, replace methyl alcohol as etherifying agent with isopropyl alcohol simultaneously, and under following reaction condition, operate:
The 8.5ml catalyst of packing into is sent into a kind of liquid mixture of being made up of 6% weight catechol and 94% isopropyl alcohol with 5g/h speed, and carrying gas flow rate is 25N ml/min, 140 ℃ of reaction temperatures.
Result of the test during catalyst is 90 hours service time is:
Catechol conversion ratio: 25%
Selectivity to monoether: 75%
Example 11
The catalyst of preparation described in example 1, with example 4 under the identical reaction condition, except reaction temperature is 200 ℃, send into hydroquinones/carbinol mixture with the speed of 1.2g/h, in the monoether reaction of hydroquinones and methyl alcohol, test.
During catalyst reacted service time in 15 hours, result of the test was:
Hydroquinones conversion ratio: 17%
Selectivity to hydroquinone monomethyl ether: 96%
Claims (4)
1. be used to prepare the method for polyhydroxy benzenes monoalky lether, above-mentioned polyhydroxy benzenes monoalky lether randomly has alkyl or halogen atom on aromatic ring, by polyhydroxy benzenes in gas phase, liquid phase or in mixing mutually with straight or branched, saturated or undersaturated, C
1-C
6Alcohol reaction is carried out, and wherein above-mentioned reaction Al: the P atomic ratio is 0.4: 1.0-1: in 1 scope, surface area is at 40-100m
2Catalyst in the/g scope forms to come catalysis, and this catalyst composition prepares with the method that may further comprise the steps:
A) from the solution of water soluble aluminum compound and water-soluble phosphorus compound, with the mixing cpd co-precipitation of Al and P;
B) under the temperature of 80-180 ℃ of scope, the drying precipitate that will obtain from step a);
C) by being heated to the final temperature of 400-800 ℃ of scope gradually from room temperature, the product that calcining obtains from step b) in air stream;
Wherein, carry out co-precipitation by regulating pH to 7.
2. the method for claim 1, it is characterized in that: the reaction of described preparation polyhydroxy benzenes monoalky lether is to carry out under the temperature of 170-220 ℃ of scope.
3. method as claimed in claim 2 is characterized in that: the reaction of described preparation polyhydroxy benzenes monoalky lether is to carry out being no more than under 200 ℃ the temperature.
4. as each described method among the claim 1-3, it is characterized in that: polyhydroxy benzenes is selected from 1,2-, 1, and 3-and 1, the 4-dihydroxy benzenes, and alcohol is selected from methyl alcohol, ethanol, propyl alcohol and isopropyl alcohol.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI2000A000685 | 2000-03-31 | ||
| IT2000MI000685A IT1318439B1 (en) | 2000-03-31 | 2000-03-31 | Preparation of aluminum and phosphorus mixed oxide catalyst involves gradual heating at specified temperature of mixed compound obtained from coprecipitation of aqueous solution of aluminum and phosphorus compounds |
| ITMI2001A000468 | 2001-03-07 | ||
| IT2001MI000468A ITMI20010468A1 (en) | 2001-03-07 | 2001-03-07 | MIXED ALUMINUM OXIDE AND PHOSPHORUS PROCEDURE FOR ITS PREPARATION AND USE AS A CATALYST |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018073743A Division CN1212192C (en) | 2000-03-31 | 2001-03-27 | Phosphorous-aluminium-mixed oxide catalyst, process for its preparation and use thereof |
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|---|---|
| CN1583262A CN1583262A (en) | 2005-02-23 |
| CN1274418C true CN1274418C (en) | 2006-09-13 |
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|---|---|---|---|
| CNB200410070562XA Expired - Lifetime CN1274418C (en) | 2000-03-31 | 2001-03-27 | Phosphorous-aluminium-mixed oxide catalyst, process for its preparation and use thereof |
| CNB018073743A Expired - Lifetime CN1212192C (en) | 2000-03-31 | 2001-03-27 | Phosphorous-aluminium-mixed oxide catalyst, process for its preparation and use thereof |
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| Application Number | Title | Priority Date | Filing Date |
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Country Status (4)
| Country | Link |
|---|---|
| CN (2) | CN1274418C (en) |
| AU (1) | AU2001256223A1 (en) |
| HK (1) | HK1052477B (en) |
| WO (1) | WO2001074485A1 (en) |
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| US11377410B2 (en) * | 2014-05-21 | 2022-07-05 | Camlin Fine Sciences Limited | Process for generating a mixed multicomponent vapor for preparation of monoalkyl ethers of diphenols |
| CN107915577B (en) * | 2016-10-08 | 2020-12-29 | 中国石油化工股份有限公司 | Method for synthesizing ethylene glycol by hydrolyzing ethylene carbonate |
| SG11202000044QA (en) | 2017-07-18 | 2020-02-27 | Shell Int Research | Process for preparing alkanediol and dialkyl carbonate |
| CN110002964B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for synthesizing o-hydroxyanisole by catalyzing catechol and methanol |
| CN110002966B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for synthesizing o-hydroxyanisole from catechol and methanol |
| CN110002965B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Production method of o-hydroxyanisole |
| CN109879729B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for producing o-hydroxyanisole |
| CN112608221B (en) * | 2020-12-11 | 2022-11-08 | 万华化学集团股份有限公司 | Preparation method of veratrole |
Family Cites Families (2)
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|---|---|---|---|---|
| JPS51105021A (en) * | 1975-03-13 | 1976-09-17 | Ube Industries | 2 kafuenooruno monoarukirueeterunoseiho |
| WO1999002260A1 (en) * | 1997-07-11 | 1999-01-21 | Shell Internationale Research Maatschappij B.V. | Catalyst composition comprising a molecular sieve and an aluminium phosphate containing matrix |
-
2001
- 2001-03-27 AU AU2001256223A patent/AU2001256223A1/en not_active Abandoned
- 2001-03-27 WO PCT/EP2001/003442 patent/WO2001074485A1/en active Application Filing
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|---|---|
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| CN1212192C (en) | 2005-07-27 |
| HK1052477A1 (en) | 2003-09-19 |
| WO2001074485A1 (en) | 2001-10-11 |
| CN1583262A (en) | 2005-02-23 |
| AU2001256223A1 (en) | 2001-10-15 |
| HK1052477B (en) | 2005-12-02 |
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