GB2056421A - Method of Preparing a Calcium Phosphate Catalyst - Google Patents
Method of Preparing a Calcium Phosphate Catalyst Download PDFInfo
- Publication number
- GB2056421A GB2056421A GB7928538A GB7928538A GB2056421A GB 2056421 A GB2056421 A GB 2056421A GB 7928538 A GB7928538 A GB 7928538A GB 7928538 A GB7928538 A GB 7928538A GB 2056421 A GB2056421 A GB 2056421A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- calcium phosphate
- phosphoric acid
- heat treatment
- test run
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/247—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by splitting of cyclic ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Disclosed is a method of preparing a calcium phosphate catalyst, which comprises reacting calcium salts with phosphoric acid salts in aqueous ammonia, separating the resulting precipitate from the reaction mixture, suitably shaping said precipitate, drying it, and subjecting to heat treatment within a temperature range of 450 to 600 DEG C in the presence of steam mixed with at least one of phosphoric acid, an aldehyde, an oxygen-containing heterocyclic compound, an alcohol, a diene hydrocarbon, an inert gas or air. The catalyst may be used in the manufacture of isoprene from isobutene and formaldehyde or by decomposition of 1,3 dioxanes as well as in alcohol dehydration reactions.
Description
SPECIFICATION
Method of Preparing a Calcium Phosphate Catalyst
The present invention relates to the production of catalysts such as can be used, for example, in the manufacture of isoprene from isobutylene and formaldehyde, and more particularly to a method of preparing a calcium phosphate catalyst for use in decomposing 1 ,3-dioxanes and, in particular, 4,4dimethyl-1 ,3-dioxane (hereinafter referred to as DMD) into isoprene, as weil as in alcohol dehydration reactions.
According to the present invention, there is provided a method of preparing a calcium phosphate catalyst, which comprises reacting calcium salts with phosphoric acid salts in aqueous ammonia, separating the resulting precipitate from the reaction mixture, suitably shaping said precipitate, drying it, and subjecting to heat treatment at high temperatures in the presence of steam, wherein according to the invention, heat treatment is performed within a temperature range of 450 to 6000C in the presence of steam mixed with phosphoric acid or aldehyde, or an oxygen-containing heterocyclic compound, or alcohol, or diene hydrocarbon, or steam mixed with an inert gas or air and phosphoric acid, or steam mixed with an inert gas and aldehyde, or an oxygen-containing compound, or alcohol, or diene hydrocarbon.
Formaldehyde and acetaldehyde are preferable to be used as said aldehydes.
It is advisable that as said oxygen-containing heterocyclic compound use is made of methyl dihydropyrane or methylene tetrahydropyrane can suitably be used.
The suitable alcohols are trimethyl carbinol and isopropenyl ethyl carbinol.
The suitable diene hydrocarbons are isoprene or piperylene.
It is also advisable that the reaction of calcium salts with phosphoric acid salts in an aqueous ammonia be carried out with the starting reactants taken in the molar ratio of 1.5:1.
The preferred embodiment is for the reaction of calcium salts with phosphoric acid salts in aqueous ammonia to be effected with the starting reactants taken in a molar ratio within 1.5:1 to 5.0:1 and for the reaction mixture obtained to be treated with a phosphoric acid solution to pH of from 5.0 to 7.0.
It is desirable to treat the reaction mixture with a phosphoric acid solution to pH of from 5.5 to 6.0.
According to the herein-proposed method, a catalyst can be obtained, featuring high selectivity (86.0 to 87.5 mole%), high activity (96.097.0%), and low coke deposition (below 1 mole%).
The aforesaid and other objects and features of the present invention are set forth in the appended claims, and the present invention will be more fully apparent from the detailed description of its embodiments presented herein under.
The proposed method of preparing a calcium phosphate catalyst can be realized as follows.
The starting reactants to be used are solutions of calcium salts, e.g. calcium chloride, and phosphoric acid salts, e.g. diammonium phosphate, disodium phosphate, etc. A suitable amount of aqua ammonia is added to the phosphoric acid salt solution prior to reacting it with the calcium salt solution for pH control of the medium.
The calcium salt and phosphoric acid salt solutions are gradually introduced into a vessel fitted with stirrer, while continuously stirring the slurry being formed. The reaction is carried out with the calcium salt and phosphoric acid salt taken in the molar ratio of 1.5:1. However, the reaction is realizable with the starting reactants having a molar ratio anywhere within the range of 1.5:1 to 5.0:1, preferably 2.5:1. In cases such as these, the reaction mixture is to be treated with a phosphoric acid solution to pH of from 5.0 to 7.0, preferably 5.5 to 6.0.
The above ranges of molar; ratios of calcium salts to phosphoric acid salts and pH values of the reaction medium are consistant with obtaining a calcium phosphate catalyst of desired structure and composition.
The resulting precipitate is separated by filtration or any other known method, washed with distilled water to remove calcium sait anions, shaped into granules by a conventional technique, and dried at a temperature between 110 and 1400C, thus obtaining a raw calcium phosphate which is then loaded for further treatment into a reactor.
The reactor is a quartz tube measuring 20 to 26 mm in diameter. The reactor is placed into an electrically heated oven for the catalyst enclosed in the reactor to be subjected to heat treatment at a temperature within 450 to 6000 C, using steam with an addition of phosphoric acid or an organic compound.
The organic compounds that may be used as additions to steam include formaldehyde, acetaldehyde, methyl dehydropyrane (MDHP), methylene tetrahydropyrane (MTHP), trimethyl carbinol (TMC), isopropenyl ethyl carbinol (IPEA), isoprene, and piperylene.
Where a calcium phosphate catalyst is obtained without pretreatment of the reaction mixture with phosphoric acid solution, heat treatment is preferably performed at 450 C.
However, where the method of calcium phosphate catalyst preparation comprises the step of treating the slurry with phosphoric acid to control the pH values of the reaction mixture to within 5.0 to 7.0, the heat treatment temperature should preferably be 5000C.
Heat treatment can also be carried out using steam mixed with an inert gas such as nitrogen, argon, etc., and with air (when phosphoric acid is added to the steam).
Steam is fed in at a space velocity of 1.0 to 2.0 h-1.
The feed rate of phosphoric acid used for catalyst heat treatment is 0.05 to 0.25 g/h per kg of catalyst.
Heat treatment times are within 2 to 50 hours, preferably between 20 and 30 hours. Space velocity for organic compound used are 0.7 to 1.5 h-', preferably 1.0 h-'.
After the catalyst has been treated with steam mixed with any one of the above-listed organic compounds or with steam mixed with an inert gas and any one of the above compounds in order to burn out the coke deposited on the catalyst surface, the catalyst is now subjected to regeneration by a mixture of steam and air at temperatures between 450 and 6000 C, preferably between 500 and 5500C. Space velocity for air ranges from 500 to 700 h-', for steam, from 1.0 to 2.0 h-l.
The calcium phosphate catalyst thus obtained has the following characteristics. DMD conversion at the level of 96 to 97%, selectivity 86.0 to 87.5 mole%, coke deposition below 1%.
The following typical examples will further illustrate certain aspects of the present invention, delineating more clearly the features and advantages specific to it.
Example 1
The starting reactants used for catalyst preparation are 1.78 1 of a calcium chloride solution containing 101.892 g of salt per 1 l of the solution and 1.6081 of a diammonium phosphate solution containing 51.02 g of salt per 1 l of the solution. An ammonia solution with a concentration of 152.15 g/l is added to the diammonium phosphate solution on the basis of having 2.33 moles of ammonia per 1 mole of diammonium phosphate immediately prior to the reaction.
The calcium chloride and diammonium phosphate solutions are gradually poured into a vessel fitted with a stirrer. The pouring procedure continues for 2 hours, the resulting slurry being continuously stirred all the while. Reaction is carried out with the solutions introduced kept practically in a constant ratio to ensure a calcium salt to phosphoric acid salt molar ratio of 2.5:1 and the slurry having a pH value within 9.0+0.05. The resultant slurry is treated with 1 50 ml of phosphoric acid concentrated to 281.26 g/i in order to reduce the pH value to 5.75.The resulting precipitate is separated from the reaction medium by filtration, washed with distilled water to remove chlorine ions, shaped into granules, and dried at ca. 1 200C. The raw calcium phosphate thus obtained is loaded, in an amount of 24 cm3, into a reactor which has the form of a quartz tube measuring 20 to 26 mm in diameter. The reactor is placed into an electrically heated oven. Steam mixed with phosphoric acid added on the basis of 0.2 g/h acid per 1 kg of catalyst is passed through the catalyst at 4000C for 30 hours.
The resulting catalyst is test run in a DMD decomposition reaction in an atmosphere of steam.
The DMD decomposition process is carried out at atmospheric pressure and a mean temperature of 3200C for the duration of 2 hours.
DMD is fed in at the rate of 24 cm3/h, and water at 48 cm3/h, which gives a DMD space velocity of 1.0 h-' and a DMD to steam dilution ratio of 1:2.
The contact cycle is followed by a regeneration cycle which comprises burning out the coke deposited on the catalyst and is to be repeated after every two hours of catalyst operation.
The regeneration cycle is carried out at 4250C, using 48 cm3/h of water and 16,800 cm3/h of air.
The catalyst is analyzed using gas-liquid chromatography techniques. The quantity of coke deposited is determined by a conventional method.
The catalyst test results are presented hereinunder in Table 1.
Example 2
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatement of the raw calcium phosphate is performed as described in Example 1, at 5000C.
The resulting catalyst is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 3
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1. Heat treatment of the raw calcium phosphate if performed as described in Example 1, at 600"C.
The resulting catalyst is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 4
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1. Heat treatment of the raw calcium phosphate is carried out at 5000C, using steam mixed with phosphoric acid added on the basis of 0.2 g/h of phosphoric acid per 1 kg catalyst and with nitrogen taken in an amount of 4800 cm3 per hour, a gas space velocity being 200 h-'.
The resulting catalyst is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 5
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1. Heat treatment of the raw calcium phosphate is carried out at 5000C, using steam mixed with phosphoric acid added on the basis of 0.2 g/h phosphoric acid per 1 kg catalyst and with air taken in an amount of 4800 cm3/h, the space velocity of air being 200 h-'.
The resulting catalyst is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 6
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1. Heat treatment of the raw calcium phosphate is carried out at 4500C, using steam with an addition of 7% by weight of aqueous solution of formaldehyde for the duration of 4 hours.
Steam space velocity (accounting for the 7% addition of the aqueous solution of formaldehyde) is 2.0 h-l.
The resultant catalyst is subjected, prior to the test run, to a procedure for burning out the coke deposited on its surface, said procedure being carried out at 5000C, using 48 cm3/h of water and 16,800 cm3/h of air.
The catalyst thus prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 7
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is performed as described in Example 6, at 5000 C.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 8
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is performed as described in Example 6, at 6000 C.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 9
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C, using steam with an addition of 5% by weight of acetaldehyde.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 10
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 4000C, using steam mixed with 7% by weight of aqueous solution of formaldehyde and with nitrogen in an amount of 4800 cm3/h, the total corresponding to a gas space velocity 200 h-' and the heat treatment procedure continuing for 4 hours.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 11
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C, using steam with an addition of 31.4% by weight of MDHP, for the duration of 2 hours. MDHP space velocity is 1.0 h-', steam space velocity, 2.0 h-'.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 12
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C, using steam with an addition of 31.6% by weight of MTHP, for the duration of 2 hours. MTHP space velocity is 1.0 h-', steam space velocity, 2.0 h-'. The resultant catalyst is subjected, prior-to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 13
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate and the coke deposit burning-out procedure that follows are carried out as described in Example 11, at 4000C.
The resultant catalyst is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 14
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate and the coke deposited burning-out procedure that follows are carried out as described in Example 11, at 6000 C.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 15
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C for 2 hours, using steam mixed with 31.4% by weight of MDHP and with nitrogen in an amount of 4800 cm3 per hour, the total corresponding to a gas space velocity of 200 h-'.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 16
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C for the duration of 2 hours, using steam mixed with 28.3% by weight of trimethyl carbinol (TMC). TMC space velocity is 1.0 h-1, that of steam, 2.0 h-' (on the liquid basis).
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 17
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C for the duration of 2 hours, using steam mixed with 30.9% by weight of isopropenyl ethyl carbinol (IPEC). IPEC space velocity is
1.0 h-', that of steam, 2.0 h-' (on the liquid basis).
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 18
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate and the coke deposit burning-out procedure that follows are carried out as described above in Example 16, at 4000C.
The resultant catalyst is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 19
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate and the coke deposit burning-out procedure that follows are carried out as described above in Example 16, at 6000C.
The resultant catalyst is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 20
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C for the duration of 6 hours, using steam mixed with 28.3% by weight TMC and that of nitrogen in an amount of 4800 cm3 per hour, the total corresponding to a gas space velocity of 200 h-1.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 21
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 4500C during 9 hours, using steam with an addition of 25.4% by weight of isoprene. Isoprene space.velocity is 1.0 h-1, that of steam, 2.0 h-' (on the liquid basis).
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 22
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate and the coke deposit burning-out procedure that follows are carried out as described above in Example 21, at 5000C.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 23
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate and the coke deposit burning-out procedure that follows are carried out as described above in Example 21, at 6000C.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 24
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C during 9 hours, using steam mixed with 25.4% by weight of isoprene and with nitrogen taken in an amount of 4800 cm3 per hour, the total corresponding to gas space velocity of 200 h-'.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 25
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 1.
Heat treatment of the raw calcium phosphate is carried out at 5000C for the duration of 9 hours, using steam mixed with 25.3% by weight of piperylene, Piperylene space velocity is 1.0 h-', that of steam, 2.0 h-'.
The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 1.
The catalyst test results are presented hereinunder in Table 1.
Example 26
The starting reactants used for catalyst preparation are 1.1 8 1 of a calcium chloride solution containing 99.8 g of calcium chloride in 11 of solution and 2.0 l of a disodium phosphate solution containing 50.21 g of salt in 11 of solution. An ammonia solution with a concentration of 1 30 g/l is added to the disodium phosphate solution on the basis of having 1.3 moles of ammonia per 1 mole of disodium phosphate immediately prior to the reaction.
The calcium chloride and disodium phosphate solutions are gradually poured into a vessel fitted with a stirrer. The pouring procedure continues for 2 hours, the resulting slurry being continuously stirred all the while. Reaction is carried out with the solutions introduced kept in a constant volume ratio to ensure a calcium chloride to disodium phosphate molar ratio of 1.5:1 and the slurry having a pH value of 9.0+0.05. The resulting precipitate is separated by filtration, washed with distilled water to remove chlorine ions, shaped into granules, and dried at a temperature of 1 200C. Heat treatment of the raw calcium phosphate is performed as described in Example 1, using a temperature of 5000C.
The catalyst so prepared is test run as described in Example 1, using a contact temperature of 375 OC. The catalyst test results are presented hereinunder in. Table 1.
Example 27
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 26.
Heat treatment of the raw calcium phosphate is carried out as described in Example 1, using a temperature of 4000 C.
The catalyst so prepared is test run as described in Example 26.
The catalyst test results are presented hereinunder in Table 1.
Example 28
The procedure used to prepare the calcium phosphate catalyst is the same as described in
Example 26.
Heat treatment of the raw calcium phosphate is performed as described in Example 6. The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described- in Example 26.
The catalyst test results-are presented hereinunder in Table 1.
Example 29
The procedure used to prepare the calcium phosphate catalyst as the same as described in
Example 26.
Heat treatment of the raw calcium phosphate is carried out as described in Example 13. The resultant catalyst is subjected, prior to the test run, to the procedure for burning out the coke deposited on its surface as described above in Example 6.
The catalyst so prepared is test run as described in Example 26.
The catalyst test results are presented hereinunder in Table 1.
In describing the above examples of embodiments of the present invention, a limited terminology has been empioyed for greater clarity. It will be understood, however, that the present invention is by no means limited by the terminology adopted herein and that each of the terms used covers all equivalent elements such as may serve the same function and be used to solve the same problems.
Although the present invention has been described herein with reference to the preferred typical embodiments thereof, it will be apparent to those skilled in the art that there may be minor modifications made in the procedures comprised in the inventive method of calcium phosphate catalyst preparation without departing from the spirit of the invention.
All such modifications and variations are contemplated to be embraced in the spirit and scope of the invention, as defined in the appended claims.
Results of Catalyst Testing in DMD Decomposition Runs
Operating temperature: 3200C
DMD volume flow rate: 1 h-'
DMD:H20 dilution ratio: 1:2
Table 1
Characteristic Values
Catalysts
as per DMD Conversion, Selectivity, Coke Formation,
Example Nos. % mole% mole%
1 2 3 4
1 97.5 86.9 1.53
2 97.2 87.2 0.84
3 96.0 87.5 0.56
4 97.4 86.9 1.04
5 97.3 86.8 1.09
6 97.5 87.0 1.50
7 97.3 87.5 0.54
8 96.0 87.3 0.47
9 97.4 87.3 0.61
10 97.4 86.9 1.58
11 97.2 87.3 0.65
12 97.2 87.2 0.69
13 97.4 86.9 1.60
14 95.9 87.5 0.48 1 5 97.3 87.2 0.80
16 97.1 87.0 0.70
17 97.0 87.2 0.68
18 97.5 86.8 1.70
19 95.8 87.4 0.46
20 97.1 86.9 0.74
21 97.4 86.9 . 1.61
22 96.8 87.1 0.63
23 95.9 87.5 0.56
24 97.0 87.0 0.72
25 96.9 87.3 0.66
26 94.7 87.2 0.59
27 95.2 86.4 1.78
28 95.0 86.6 0.52
29 94.8 87.0 0.50
30 94.7 86.8 0.52
31 94.9 86.6 0.58
Claims (13)
- Claims 1. A method of preparing a calcium phosphate catalyst, which comprises reacting calcium salts with phosphoric acid salts in aqueous ammonia, separating the resulting precipitate from the reaction mixture thus obtained, suitably shaping said precipitate, drying it, and subjecting to heat treatment within a temperature range of 450 to 6000C in the presence of steam mixed with at least one of the components selected from the group consisting of an inert gas, air, phosphoric acid, aldehyde, an oxygen-containing heterocyclic compound, alcohol, and diene hydrocarbon.
- 2. A method according to Claim 1, in which the aldehyde used is acetaldehyde.
- 3. A method according to Claim 1, in which the oxygen-containing heterocyclic compound used is methyl dehydropyrane.
- 4. A method according to Claim 1, in which the oxygen-containing heterocyclic compound used is methylene tetrahydropyrane.
- 5. A method according to Claim 1, in which the alcohol used is trimethyl carbinol.
- 6. A method according to Claim 1, in which the alcohol used is isopropenyl ethyl carbinol.
- 7. A method according to Claim 1, in which the diene hydrocarbon used is isoprene.
- 8. A method according to Claim 1, in which the diene hydrocarbon used is piperylene.
- 9. A method according to Claim 1 , wherein the reaction between calcium salts and phosphoric acid salts in aqueous ammonia is effected with the starting reactants taken in the molar ratio of 1.5:1.
- 10. A method according to Claim 1, wherein, the reaction between calcium salts and phosphoric acid salts in aqueous ammonia is effected with the starting reactants taken in a molar ratio within the range of 1.5:1 to 5.0:1, and the reaction mixture obtained is treated with a solution of phosphoric acid to pH of from 5.0 to 7.0.
- 11. A method according to Claim 7, wherein the reaction mixture is treated with a solution of phosphoric acid to pH of from 5.5 to 6.0.
- 12. A method according to Claims 1 through 11, substantially, as described in the foregoing examples.
- 13. A catalyst, whenever produced by the method claimed in any one of the preceding claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7928538A GB2056421B (en) | 1979-08-16 | 1979-08-16 | Method of preparing a calcium phosphate catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7928538A GB2056421B (en) | 1979-08-16 | 1979-08-16 | Method of preparing a calcium phosphate catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2056421A true GB2056421A (en) | 1981-03-18 |
| GB2056421B GB2056421B (en) | 1983-04-27 |
Family
ID=10507240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7928538A Expired GB2056421B (en) | 1979-08-16 | 1979-08-16 | Method of preparing a calcium phosphate catalyst |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2056421B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021173738A1 (en) | 2020-02-28 | 2021-09-02 | The Procter & Gamble Company | Method to remove chemical contaminants |
-
1979
- 1979-08-16 GB GB7928538A patent/GB2056421B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021173738A1 (en) | 2020-02-28 | 2021-09-02 | The Procter & Gamble Company | Method to remove chemical contaminants |
| WO2021173739A1 (en) | 2020-02-28 | 2021-09-02 | The Procter & Gamble Company | Method of using nanofiltration and reverse osmosis to remove chemical contaminants |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2056421B (en) | 1983-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4624937A (en) | Process for removing surface oxides from activated carbon catalyst | |
| US4696772A (en) | Amine oxidation using carbon catalyst having oxides removed from surface | |
| EP0232182B1 (en) | Process for producing bases | |
| EP0246272B1 (en) | Silica-titania hydrocarbon conversion catalyst | |
| US4246247A (en) | Method of preparing a calcium phosphate catalyst | |
| GB2056421A (en) | Method of Preparing a Calcium Phosphate Catalyst | |
| US3846338A (en) | Method for producing phosphate catalyst | |
| KR920003219B1 (en) | Process for the production of zeolite | |
| KR900003952B1 (en) | Process for the production of dienes from aldehydes using improved boron phosphate catalyst | |
| US4961914A (en) | Method of preparing hydrogen cyanide | |
| US4298503A (en) | Method of preparing calcium boron phosphate catalyst | |
| GB2073161A (en) | Method of Preparing Calcium Boron Phosphate Catalyst | |
| US5770757A (en) | Ammoxidation catalysts containing germanium to produce high yields of acrylonitrile | |
| US4014952A (en) | Process for the preparation of isoprene | |
| CA1141369A (en) | Method of preparing calcium boron phosphate catalyst | |
| CA1143717A (en) | Catalyst for decomposition of 1,3-dioxanes | |
| US4323479A (en) | Catalyst for decomposition of 1,3-dioxanes | |
| GB2080134A (en) | Catalysts for condensation, dehydration and decomposition reactions | |
| GB2053871A (en) | Method for producing calcium phosphate catalyst | |
| JPS5838227A (en) | Preparation of aldehyde | |
| SU1115794A1 (en) | Catalyst for incomplete oxidation of propane and method of its preparation | |
| JP2855914B2 (en) | Method for producing dialkylnaphthalene | |
| SU1657223A1 (en) | Method of producing catalyst for isomerization of pentene-2 | |
| SU1366520A1 (en) | Method of obtaining silica filler | |
| IE45340B1 (en) | An ammoxidation catalyst and its use in the preparation of4cyanothiazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |