CN1583262A - 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
- Publication number
- CN1583262A CN1583262A CNA200410070562XA CN200410070562A CN1583262A CN 1583262 A CN1583262 A CN 1583262A CN A200410070562X A CNA200410070562X A CN A200410070562XA CN 200410070562 A CN200410070562 A CN 200410070562A CN 1583262 A CN1583262 A CN 1583262A
- Authority
- CN
- China
- Prior art keywords
- temperature
- catalyzer
- under
- reaction
- benzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 title abstract description 29
- 238000002360 preparation method Methods 0.000 title description 16
- 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 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- -1 aluminum compound Chemical class 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000002156 mixing Methods 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 3
- 150000001346 alkyl aryl ethers Chemical class 0.000 abstract description 2
- 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
- 150000008442 polyphenolic compounds Polymers 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 14
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000001301 oxygen Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229960003742 phenol Drugs 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
- 150000001298 alcohols Chemical class 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000001556 precipitation Methods 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
- 230000003245 working effect Effects 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012856 packing 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
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 238000004090 dissolution Methods 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
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 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
- 239000006200 vaporizer Substances 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
The invention relates to an A1 and P mixed oxide catalyst, the preparing method and use thereof. In particular, the invention relates to a method for preparing polyhydroxy phenol monoalkyl ether. Wherein the A1 and P mixed oxide used with a surface area of 50-100 m2/g is prepared by heating a mixed compound gradually to 400-800 deg C, and the mixed compound is obtained by coprecipitation from an aqueous solution of an A1 and P compound. The A1 and P mixed oxide catalyst can be advantageously used as a monoalkylation catalyst for 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-benzene monoalky lether.
Background technology
Diphenol monoalkyl ethers such as hydroxyanisole (1-methoxyl group-2-hydroxybenzene) and Pyrocatechol monoethyl ether (guetol, 1-oxyethyl group-2-hydroxybenzene) and other diphenol monoalkyl ethers, can prepare by the condensation reaction (etherificate) of pyrocatechol 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 Sauerstoffatom place.This reaction can be carried out in gas phase, liquid phase or mixed phase, and preferred alkylating agent is corresponding alcohol.
Disclosed catalyst system 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 conditions.For fear of this problem, the volatile compound of B and/or P is feed simultaneously, in case active ingredient is lost by sublimation under reaction conditions.Alternatively, active reduction can be avoided by increasing temperature of reaction, yet, increase temperature of reaction and cause desired product selectivity decline.In addition, the dissemination gradually of active phase has reduced the physical strength of catalyzer 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 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 catalyzer 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 alkalimetal ion (normally potassium) can also be added in the composition and (press the 0-0.9 ratio).Compare with the catalyst system 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 catalyzer is characterized in that: in temperature range is 300-600 ℃, preferably under 400 ℃, carries out after the last thermal treatment, and specific surface area is at 30-50m
2In the scope of/g.It is etherification reaction under 200-400 ℃ that this catalyzer is used for described temperature range.Should emphasize, according to above-mentioned patent, be provided with Ti or Si in catalyzer is formed, this causes the selectivity to hydroxyanisole (etherificate that is used for pyrocatechol and methyl alcohol) to reduce, and especially, causes catalytic activity significantly to reduce.In fact, under 280 ℃ of temperature, transformation efficiency reduces, and from 64.7% to 46.3% (catalyzer that does not have Ti) is to 55.7% (catalyzer that does not have Si); Selectivity reduces, and from 98.3% to 95.8% (catalyzer that does not have Ti) is to 97.4% (catalyzer that does not have Si).
In view of the foregoing, very be desirable to provide a kind of catalyzer, its specific activity is above-mentioned or known catalysts is bigger, so that operate under the reaction conditions of milder, from then on provides the qualified transformation efficiency that monoether class (for example hydroxyanisole) is had high selectivity.An ideal system should be to operate under than the lower temperature of reaction of the temperature of reaction 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 based on Al/P/O, this catalyst system according to the preparation of technology different described in the patent documentation, and this catalyst system compares with the prior art system, has the following advantages:
1) specific surface 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 surface area be significantly higher than described in the document and under uniform temp the specific surface 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 surface 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 activity.As a result, can the lower catalyzer of preparation cost with simpler method, these methods have better circulation ratio, 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 catalyzer of method of the present invention preparation, and therefore aspect desired product selectivity and catalyst themselves work-ing 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 pyrocatechol transformation efficiency is 20-30%, and reaction surpasses 1,300 hour to flow process simultaneously, and the selectivity of hydroxyanisole 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 catalyzer, this catalyzer is used for by reaction between polyhydroxy-benzene compounds and the alcohol polyhydroxy-benzene being carried out oxygen monoalkylation (monoetherization), more particularly, is used for dihydroxy-benzene 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 mixed phase, carry out, the high conversion that has the reagent of qualification simultaneously, with to oxygen monoalkylated product (1-alkoxyl group-2-hydroxybenzene, 1-methoxyl group-2-hydroxybenzene or hydroxyanisole for example) has highly selective, and, have low selectivity such as the complete product (for example veratrole) of etherificate to other undesired products.Another advantage of catalyzer of the present invention is: reaction can be carried out very time long lifetime and not make catalyzer passivation aspect active and selectivity; There is no need to allow compound with reagent while feed, constant with the performance of catalyst themselves after keeping after a while.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, catalyzer 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 vapor, so the existence of B and/or P-compound can cause undesirable corrosive nature in the downstream of reactor itself.
Catalyzer 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 property (in the yield aspects of the selectivity and the product of wanting) at least between 1,300 hour reaction period.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 catalyst body 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.
Catalyzer of the present invention is made up of aluminum 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 themselves in the catalyzer composition.
The preparation of catalystic material of the present invention is to make the compound co-precipitation of Al and P, obtains the precursor of final catalyzer.Generally, preparation is to begin to carry out with water soluble aluminum compound and water-soluble phosphorus compound.With these two kinds of compound dissolutions, 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 catalyzer 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 catalyzer 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 oxygen-containing 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 aluminum chlorides and 85%-phosphoric 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 basic cpd simultaneously.
Throw out general (but be not must) is gel form, and throw out 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 catalyzer net shape can be any shape that is adapted at using in the fixed-bed reactor, as extrudate, pellet or the saccharoid 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 thermal treatment according to the amount of the catalyzer of preparation.
Thermal treatment must promote the removal of volatile compound according to known industrial practice.It is mandatory that this is that preparation has a catalyzer institute of high surface area 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 oxyhydroxide is perhaps also used four-C
1-C
4Alkyl ammonium hydroxide is as precipitation agent.
This method provides to be had specific surface 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 catalyzer 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 mashed prod drying, compression molding with under 400 ℃ of temperature, in air, calcine at last.Like this, this method comprises does not have consoluet Al reagent, and so and final compound is influenced by the original property 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 catalyzer of the present invention, especially in the final compound after thermal 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 work-ing life, refers to that katalysis keeps the sufficiently stable time between twice regeneration in succession this work-ing life.This is because the dissemination of granules of catalyst (extrudate or pellet) and because due to carbon product or pitch precipitates on the surface of catalyst themselves.
Under catalyzer situation of the present invention,, can carry out hot manipulation of regeneration when being deposited on owing to carbon product or pitch when on the catalyzer passivation taking place.Typical manipulation of regeneration can be under 450-650 ℃ of temperature, is more easily under 650 ℃ of temperature, carries out in airflow.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 manipulation of regeneration can not cause and the live catalyst change on the specific characteristic mutually.
By diphenols or generally be the reactivity of the prepared catalyzer of the etherificate of polyhydroxy-benzene, with the laboratory flow reactor analysis that the shape catalyzer of wanting is housed.Particularly, these reagent (diphenols and alcohol) can be chosen in the vaporizer 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.Temperature of reaction can be in 170-220 ℃ of scope, is to remain in the 180-200 ℃ of scope more easily.
Reagent can be: i) about polyhydroxy-benzene, pyrocatechol, Resorcinol or Resorcinol (diphenols), also be 1,2-, 1,3-and 1,4-dihydroxy-benzene, perhaps these reagent can have substituent such as methyl or halogen atom on ring, ii) about alcohols, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and other carbonatomss alcohols up to 6, these alcohols may optionally be undersaturated condition.
Test is the 7.5ml catalyzer of packing in the microreactor of laboratory, sends into the liquid mixture that contains 50% weight pyrocatechol and 50% methyl alcohol with 3g/h, and carries out under the specific gas flow rate of 35Nml/min.Temperature of reaction 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 mashed prod by suction.Then mashed prod is placed in the static drying machine, drying is 12 hours under 120 ℃, so that the white mass that obtains doing, then white mass is at high temperature handled in airflow, and adopt following timetable: the temperature rise 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 temperature rise 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 saccharoid of median size 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 thermal 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 thermal treatment, the Al/P ratio in final catalyst is 0.95 ± 0.04.
Example 4
Under above-mentioned reaction conditions, will in the monoether reaction of pyrocatechol and methyl alcohol, test as prepared catalyzer as described in the example 1.Particularly, temperature of reaction is 190 ℃.Resulting test-results in the life period of reaction in whole 1300 hours gathers and lists in the table.
Example 5
Catalytic test is under the reaction conditions identical with example 4, except temperature of reaction is 200 ℃, carries out on the catalyzer that makes described in example 1.
Reference examples 6
Catalytic test is under the reaction conditions identical with example 4, except temperature of reaction is 275 ℃, carries out on the catalyzer that makes described in example 1.
Reference examples 7
Catalytic test is under the reaction conditions identical with example 4, except temperature of reaction is 275 ℃, carries out on the catalyzer that makes described in example 2.
Reference examples 8
Catalytic test is under the reaction conditions identical with example 4, except temperature of reaction is 275 ℃, carries out on the catalyzer that makes described in example 3.
Table
Catalyzed reaction test in the pyrocatechol monoalkylation
| Example/catalyzer | T，℃ | * reaction times hour | The pyrocatechol transformation efficiency, % | To the selectivity of hydroxyanisole, % |
| ????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 |
* the reaction times 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.Test-results at 600 hours catalytic life time durations is:
Pyrocatechol transformation efficiency: 24%
Selectivity to Pyrocatechol monoethyl ether (guetol): 96%
From top indicated test, can prove:
1) catalyzer described in the example 1 kept its reactive characteristics at least 1300 hours, and transformation efficiency is higher than 20% and be 99.1%-99.2% (reactive example 4) to the selectivity of hydroxyanisole simultaneously.
2) catalyzer shows described in the example 1, and when testing under surpassing 200 ℃ temperature, loss is to the selectivity of hydroxyanisole; More particularly, (also once reporting in EP 509,927 examples) under 275 ℃ of temperature, selectivity drops to 96.54% (reactive reference examples 6).
3) catalyzer 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 catalyzer described in the example 1.
4) catalyzer described in the reference examples 3, the Al/P ratio that it is characterized in that catalyzer in Al/P ratio and example 1 and 2 is significantly different, it has the catalytic performance than the remarkable variation of catalyzer of the present invention, mainly is in variation aspect the selectivity of hydroxyanisole (reactive reference examples 8).
Example 10
Follow the step of example 4, replace methyl alcohol as etherifying agent with Virahol simultaneously, and under following reaction conditions, operate:
The 8.5ml catalyzer of packing into is sent into a kind of liquid mixture of being made up of 6% weight pyrocatechol and 94% Virahol with 5g/h speed, and the delivering gas flow velocity is 25Nml/min, 140 ℃ of temperature of reaction.
Test-results during catalyzer is 90 hours duration of service is:
Pyrocatechol transformation efficiency: 25%
Selectivity to monoether: 75%
Example 11
The catalyzer of preparation described in example 1, with example 4 under the identical reaction conditions, except temperature of reaction is 200 ℃, send into Resorcinol/carbinol mixture with the speed of 1.2g/h, in the monoether reaction of Resorcinol and methyl alcohol, test.
During catalyzer reacted duration of service in 15 hours, test-results was:
Resorcinol transformation efficiency: 17%
Selectivity to hydroquinone monomethyl ether: 96%
Claims (4)
1. be used to prepare the method for polyhydroxy-benzene monoalky lether, above-mentioned polyhydroxy-benzene monoalky lether randomly has alkyl or halogen atom on aromatic ring, by polyhydroxy-benzene in gas phase, liquid phase or mixed phase with straight or branched, saturated or undersaturated, C
1-C
6Alcohols reacts and carries out, and wherein above-mentioned its Al of reaction: the P atomic ratio is 0.4: 1.0-1: in 1 scope, surface-area is at 40-100m
2Catalyzer in the/g scope forms to come catalysis, and this catalyzer 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 be heated to the outlet temperature of 400-800 ℃ of scope gradually from room temperature, the product that calcining obtains from step b) in airflow wherein, carries out co-precipitation by regulating pH to 7.
2. the method for claim 1, it is characterized in that: described reaction is to carry out under the temperature of 170-220 ℃ of scope.
3. method as claimed in claim 2 is characterized in that: described reaction 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-benzene is selected from 1,2-, 1, and 3-and 1, the 4-dihydroxy-benzene, and alcohol is selected from methyl alcohol, ethanol, propyl alcohol and Virahol.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1583262A true CN1583262A (en) | 2005-02-23 |
| CN1274418C CN1274418C (en) | 2006-09-13 |
Family
ID=26332735
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018073743A Expired - Lifetime CN1212192C (en) | 2000-03-31 | 2001-03-27 | Phosphorous-aluminium-mixed oxide catalyst, process for its preparation and use thereof |
Country Status (4)
| Country | Link |
|---|---|
| CN (2) | CN1274418C (en) |
| AU (1) | AU2001256223A1 (en) |
| HK (1) | HK1052477B (en) |
| WO (1) | WO2001074485A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879729A (en) * | 2019-02-21 | 2019-06-14 | 宝鸡文理学院 | A method of producing ortho-hydroxyanisole |
| CN110002966A (en) * | 2019-02-21 | 2019-07-12 | 宝鸡文理学院 | A kind of method of catechol and methanol-fueled CLC ortho-hydroxyanisole |
| CN110002964A (en) * | 2019-02-21 | 2019-07-12 | 宝鸡文理学院 | A method of catalysis catechol and methanol-fueled CLC ortho-hydroxyanisole |
| CN110002965A (en) * | 2019-02-21 | 2019-07-12 | 宝鸡文理学院 | A kind of production method of ortho-hydroxyanisole |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3145901B1 (en) | 2014-05-21 | 2021-08-18 | 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 |
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 WO PCT/EP2001/003442 patent/WO2001074485A1/en active Application Filing
- 2001-03-27 AU AU2001256223A patent/AU2001256223A1/en not_active Abandoned
- 2001-03-27 CN CNB200410070562XA patent/CN1274418C/en not_active Expired - Lifetime
- 2001-03-27 CN CNB018073743A patent/CN1212192C/en not_active Expired - Lifetime
-
2003
- 2003-07-08 HK HK03104846.5A patent/HK1052477B/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879729A (en) * | 2019-02-21 | 2019-06-14 | 宝鸡文理学院 | A method of producing ortho-hydroxyanisole |
| CN110002966A (en) * | 2019-02-21 | 2019-07-12 | 宝鸡文理学院 | A kind of method of catechol and methanol-fueled CLC ortho-hydroxyanisole |
| CN110002964A (en) * | 2019-02-21 | 2019-07-12 | 宝鸡文理学院 | A method of catalysis catechol and methanol-fueled CLC ortho-hydroxyanisole |
| CN110002965A (en) * | 2019-02-21 | 2019-07-12 | 宝鸡文理学院 | A kind of production method of ortho-hydroxyanisole |
| CN110002966B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for synthesizing o-hydroxyanisole from catechol and methanol |
| CN110002964B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for synthesizing o-hydroxyanisole by catalyzing catechol and methanol |
| CN109879729B (en) * | 2019-02-21 | 2022-04-19 | 宝鸡文理学院 | Method for producing o-hydroxyanisole |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2001256223A1 (en) | 2001-10-15 |
| CN1274418C (en) | 2006-09-13 |
| CN1212192C (en) | 2005-07-27 |
| HK1052477A1 (en) | 2003-09-19 |
| CN1420805A (en) | 2003-05-28 |
| HK1052477B (en) | 2005-12-02 |
| WO2001074485A1 (en) | 2001-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1077882C (en) | Process for preparation for alkanolamine, catalyst used in process for preparation of catalyst | |
| US9012351B2 (en) | Method for continuously preparing metal oxides catalyst and apparatus thereof | |
| CN1913967A (en) | Method for making mesoporous or combined mesoporous and microporous inorganic oxides | |
| CN1115298C (en) | Y-type molecular sieve and its prepn. | |
| CN1180872C (en) | Catalyst for decomposing N2O, its use and method for prodn. thereof | |
| CN1512914A (en) | Process for production of catalysts with improved accessibility | |
| CN88101443A (en) | The preparation method of aromatic hydrocarbon | |
| CN110142061A (en) | Hud typed P-CoFe2O4The preparation method and applications of@GCN photochemical catalyst | |
| CN1274418C (en) | Phosphorous-aluminium-mixed oxide catalyst, process for its preparation and use thereof | |
| CN103638963A (en) | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof | |
| CN101039892A (en) | Catalysts for cycloalkanes oxidation and decomposition of cycloalkyl hydroperoxide | |
| CN101531517B (en) | Method for preparing composite material of silicon carbide of biological appearance and molecular sieve | |
| CN107497473B (en) | Preparation method of Y molecular sieve catalyst with cordierite as carrier | |
| CN112206820B (en) | Composite metal oxide catalyst for preparing isobutyl isobutyrate by using isobutyraldehyde one-step method and preparation method thereof | |
| CN1147421A (en) | Process for preparation of micro-mesoporous gel | |
| CN1142022C (en) | Transalkylation catalyst and its prepn. | |
| CN1157283A (en) | Process for production of alkyl ether of phenol and catalyst used therein | |
| CN1502596A (en) | Process for preparing phenol by dihydroxy-benzene hydro-deoxygenation | |
| CN1611300A (en) | Quasi-thin empholite composition containing organic reaming agent | |
| CN1072648C (en) | Process for preparation of amides from oximes | |
| CN108658728A (en) | Application of the titanium Si-Al molecular sieve in preparing propylene glycol | |
| CN1240654C (en) | Method for preparing 2,6-dimethylphenol | |
| CN107497479B (en) | Method for preparing methoxy methyl acetate by using cordierite as carrier to synthesize β molecular sieve | |
| CN101148436B (en) | Catalytic synthesis method for pyridine base | |
| CN1047960C (en) | Catalyst for ammoniation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: CFS-EUROPE LIMITED Free format text: FORMER NAME: BORREGAARD ITALIA S.P.A. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Milan Italy Patentee after: CFS Europe Ltd Address before: Milan Italy Patentee before: Borregaard Italia S. P. A. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060913 |