CN101658790B - Method for preparing dehydrogenation catalyst - Google Patents
Method for preparing dehydrogenation catalyst Download PDFInfo
- Publication number
- CN101658790B CN101658790B CN200810119051.0A CN200810119051A CN101658790B CN 101658790 B CN101658790 B CN 101658790B CN 200810119051 A CN200810119051 A CN 200810119051A CN 101658790 B CN101658790 B CN 101658790B
- Authority
- CN
- China
- Prior art keywords
- content
- rare earth
- oxide
- dehydrogenation
- cerium oxide
- 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.)
- Active
Links
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title abstract description 9
- 238000000034 method Methods 0.000 title abstract description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 64
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 61
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 54
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- -1 silicate calcium salt Chemical class 0.000 claims abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 44
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 23
- 229940072033 potash Drugs 0.000 claims description 23
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 23
- 235000015320 potassium carbonate Nutrition 0.000 claims description 23
- 239000000395 magnesium oxide Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 13
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000007493 shaping process Methods 0.000 claims description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 9
- 238000004898 kneading Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 27
- 229910052918 calcium silicate Inorganic materials 0.000 description 24
- 235000012241 calcium silicate Nutrition 0.000 description 24
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 24
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 24
- 235000019976 tricalcium silicate Nutrition 0.000 description 24
- 235000012245 magnesium oxide Nutrition 0.000 description 20
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 16
- 229910052684 Cerium Inorganic materials 0.000 description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 11
- 235000013980 iron oxide Nutrition 0.000 description 11
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical group [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing a dehydrogenation catalyst, which comprises the following steps of: (a) measuring the content of specific components of rare earth containing cerium oxide; (b) adding iron oxide and/or an iron oxide precursor, potassium oxide and/or a potassium oxide precursor, a silicate calcium salt and a pore-forming material into the rare earth, and mixing the materials to form a mixture; (c) mixing the mixture with a proper amount of water, kneading the mixture sufficiently, and extruding the mixture into bars to obtain preforms; and (d) drying and calcinating the preforms to obtain the finished product of the dehydrogenation catalyst, wherein the specific components to be measured in the step (a) comprise the cerium oxide in the rare earth and the compounds which are the same as the materials added in the step (b). The method for preparing the dehydrogenation catalyst has the advantages of no pollution and low cost.
Description
Technical field
The invention belongs to the dehydrogenation field, relate to specifically contain the Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst field of cerium.
Background technology
In the Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst field, conversion ratio and dehydrogenation optionally improve the selection that depends primarily on dehydrogenation.The tradition dehydrogenation mainly comprises the dehydrogenation that contains chromium and contain two series of cerium, but because chromium is carcinogen, can cause environmental pollution, be very restricted in industrial production, the dehydrogenation that therefore contains at present cerium becomes the main object of people's research and production.
The process for preparing the dehydrogenation that contains cerium oxide in prior art is, compound and some additives of the elements such as cerous nitrate and iron, potassium, molybdenum are mixed, through obtaining the finished product dehydrogenation after kneading, calcining and other processes, decomposition reaction occurs in the cerous nitrate in the original mixed material in calcination process, finally form the active component cerium oxide in dehydrogenation.But in prior art, there is following defective in the preparation process of dehydrogenation: (1) cerous nitrate can decompose a large amount of nitrogen oxide of generation when calcining, and these materials can cause serious pollution to environment; (2) in prior art people in the selection course of dehydrogenation raw material, for the ease of constituent analysis, and avoid introducing the impurity that may cause reducing the dehydrogenation activity, the raw material that the active component cerium oxide is corresponding often only limits to can be at the chemical pure cerous nitrate of pyrolytic, and commercially available chemical pure cerous nitrate normally prepares through the multi-grade chemical purification process from the rare earth that contains cerium oxide, make the cerous nitrate price higher, thereby cause the cost of dehydrogenation higher.In addition, be decomposed into as far as possible cerium oxide in order to ensure cerous nitrate, calcining heat needs 800-1000 ℃ usually, and energy consumption is larger.
Summary of the invention
For this reason, technical problem to be solved by this invention is: overcome the defective seriously polluted in the dehydrogenation preparation method in prior art, that product cost is high, the preparation method of the dehydrogenation that a kind of preparation process is pollution-free, product cost is low is provided.
for solving the problems of the technologies described above, the invention provides a kind of preparation method of dehydrogenation, comprise the steps: that (a) measures the special component content of the rare earth that contains cerium oxide, (b) add iron oxide and/or iron oxide predecessor in the described rare earth that contains cerium oxide, potassium oxide and/the potassium oxide predecessor, calsil, pore creating material, mix rear formation compound, in described compound, described cerium oxide weight percentage is 1-30wt%, described iron oxide and/or iron oxide precursor amounts are 40-80wt%, described potassium oxide and/the potassium oxide precursor amounts is 5-25wt%, described calsil content is 10-30wt% (adding the total amount in rare earth), described Content of Pore-forming Agents is 1-5wt%, surplus is non-oxide cerium and the impurity different from adding material in described rare earth, (c) described compound is mixed with suitable quantity of water, fully mediate, then obtain article shaped after extrusion, (d) described article shaped is first carried out drying, then obtains the dehydrogenation finished product after calcining, wherein, the described special component that needs in step (a) to measure be in described rare earth cerium oxide and in step (b) with the described identical compound of material that adds.
In step (b), also add magnesia and/or magnesia predecessor, its content 1-10wt% in described mixture.Cerium oxide content described in described compound is 10-20wt%, and described iron oxide and/or iron oxide precursor amounts are 60-70wt%.In described rare earth, cerium oxide content is 5-35wt%.In described rare earth, cerium oxide content is preferably 15-20wt%.Wherein, described pore creating material is one or more in sodium carboxymethylcellulose, sesbania powder, cellulose powder.Described potassium oxide predecessor is potash and/or saleratus.
In step (d), described calcining heat is 500-1000 ℃, calcines 5-250 minute, and described calcining heat is preferably 600-800 ℃.Also comprise the shaping process after described calcining.
Compared with prior art the present invention has the following advantages:
(1) directly adopt the rare earth that contains as the cerium oxide of active component in the raw material of preparation dehydrogenating agent, therefore in the process of preparation dehydrogenation, produce a large amount of pernicious gases when avoiding in prior art cerous nitrate to decompose, to the situation of environment, make that preparation process cleans more, environmental protection.
(2) adopt the cheap Rare Earth Mine that contains cerium oxide as raw material, avoid the chemical pure cerous nitrate that uses price more expensive, can greatly reduce the preparation cost of dehydrogenation.In addition, because Ce elements in the raw material that adds exists with the form of cerium oxide, do not need the process through pyrolytic, therefore compared with prior art, the calcining heat in preparation process can reduce 100-200 ℃, can reduce a part of energy consumption.
The specific embodiment
Embodiment 1
At first cerium oxide, iron oxide, potash, magnesia, dicalcium silicate, tricalcium silicate, carboxymethylcellulosodium sodium content in the rare earth that contains cerium oxide are measured, thereby can be according to the content of each raw material in compound in next step, need to determine the amount of rare earth and the amount that need to add each raw material in the rare earth.Obtain that in rare earth, cerium oxide content is 20wt%.
Next add potash, iron oxide, magnesia, dicalcium silicate, tricalcium silicate, sodium carboxymethylcellulose in described rare earth, obtain compound and make in compound after fully mixing, cerium oxide content is 10wt%, iron oxide content is 60wt%, potash content is 15wt%, and dicalcium silicate, tricalcium silicate total content are 10wt%, and content of magnesia is 3wt%, carboxymethylcellulosodium sodium content is 1wt%, and surplus is non-oxide cerium and the impurity different from adding material in rare earth.Wherein, potash can generate the active material potassium oxide after calcining; Iron oxide mainly plays skeleton function in the finished product dehydrogenation, in raw material, ferric oxide particles through the continuous sintering of calcining, final generates the iron oxide skeleton structure with pore structure, just active component such as cerium oxide, potassium oxide load are thereon; Magnesia in raw material plays as the structural reinforcing agent effect that increases the final resistance to compression impact strength of dehydrogenation finished product; The effect that dicalcium silicate, tricalcium silicate can play plastotype, gain in strength, in the process of large-scale production dehydrogenation, usually can adopt cheap cement to replace calsil, and can not affect the catalytic effect of dehydrogenation, the main component of commercially available cement is calsil, aluminum calcium salt, iron oxide and a little impurity; Sodium carboxymethylcellulose is pore creating material.
Again above-mentioned compound is mixed with suitable quantity of water, put into kneader and fully mediate, then put into banded extruder obtain the bar shaped article shaped after extrusion.
At last the bar shaped article shaped is positioned over and is dried under air at room temperature that in article shaped, moisture volatilizees substantially, then after 180 minutes, can obtain dehydrogenation finished product E1 through shaping in calcining under 700 ℃.
Embodiment 2
At first cerium oxide, iron oxide, potash, saleratus, dicalcium silicate, tricalcium silicate, sesbania content in the rare earth that contains cerium oxide are measured, thereby can be according to the content of each raw material in compound in next step, need to determine the amount of rare earth and the amount that need to add each raw material in the rare earth.Obtain that in rare earth, cerium oxide content is 15wt%.
Next add potash, saleratus, iron oxide, dicalcium silicate, tricalcium silicate, sesbania in described rare earth, obtain compound and make in compound after fully mixing, cerium oxide content is 15wt%, iron oxide content is 40wt%, potash, saleratus total content are 25wt%, dicalcium silicate, tricalcium silicate total content are 18wt%, and sesbania content is 1wt%, and surplus is non-oxide cerium and the impurity different from adding material in rare earth.
Again above-mentioned compound is mixed with suitable quantity of water, put into kneader and fully mediate, then put into banded extruder obtain the bar shaped article shaped after extrusion.
At last the bar shaped article shaped is positioned over and is dried under air at room temperature that in article shaped, moisture volatilizees substantially, then after 120 minutes, can obtain dehydrogenation finished product E2 through shaping in calcining under 1000 ℃.
Embodiment 3
At first cerium oxide, iron oxide and ferric carbonate, potash, magnesia, dicalcium silicate, tricalcium silicate, cellulose powder content in the rare earth that contains cerium oxide are measured, thereby can be according to the content of each raw material in compound in next step, need to determine the amount of rare earth and the amount that need to add each raw material in the rare earth.Obtain that in rare earth, cerium oxide content is 15wt%.
Next add potash, iron oxide and ferric carbonate, magnesia, dicalcium silicate, tricalcium silicate, cellulose powder in described rare earth, obtain compound and make in compound after fully mixing, cerium oxide content is 5wt%, iron oxide and ferric carbonate total content are 70wt%, potash content is 5wt%, and content of magnesia is 1wt%, and dicalcium silicate, tricalcium silicate total content are 13wt%, cellulose powder content is 5wt%, and surplus is non-oxide cerium and the impurity different from adding material in rare earth.
Again above-mentioned compound is mixed with suitable quantity of water, put into kneader and fully mediate, then put into banded extruder obtain the bar shaped article shaped after extrusion.
At last the bar shaped article shaped is positioned over and is dried under air at room temperature that in article shaped, moisture volatilizees substantially, then after 250 hours, can obtain dehydrogenation finished product E3 through shaping in calcining under 600 ℃.
Embodiment 4
At first cerium oxide, iron oxide, potassium oxide, magnesia, dicalcium silicate, tricalcium silicate, carboxymethylcellulosodium sodium content in the rare earth that contains cerium oxide are measured, thereby can be according to the content of each raw material in compound in next step, need to determine the amount of rare earth and the amount that need to add each raw material in the rare earth.Obtain that in rare earth, cerium oxide content is 5wt%.
Next add potassium oxide, iron oxide, magnesia, dicalcium silicate, tricalcium silicate, sodium carboxymethylcellulose in described rare earth, obtain compound and make in compound after fully mixing, cerium oxide content is 1wt%, iron oxide content is 80wt%, potassium oxide content is 5wt%, and content of magnesia is 1wt%, and dicalcium silicate, tricalcium silicate total content are 10wt%, described Content of Pore-forming Agents is 2wt%, and surplus is non-oxide cerium and the impurity different from adding material in rare earth.
Again above-mentioned compound is mixed with suitable quantity of water, put into kneader and fully mediate, then put into banded extruder obtain the bar shaped article shaped after extrusion.
At last the bar shaped article shaped is positioned over and is dried under air at room temperature that in article shaped, moisture volatilizees substantially, then after 5 minutes, can obtain dehydrogenation finished product E4 through shaping in calcining under 800 ℃.
Embodiment 5
At first cerium oxide, iron oxide, potash, magnesia, dicalcium silicate, tricalcium silicate, cellulose powder content in the rare earth that contains cerium oxide are measured, thereby can be according to the content of each raw material in compound in next step, need to determine the amount of rare earth and the amount that need to add each raw material in the rare earth.Obtain that in rare earth, cerium oxide content is 35wt%.
Next add potash, iron oxide, magnesia, dicalcium silicate, tricalcium silicate, cellulose powder in described rare earth, obtain compound and make in compound after fully mixing, cerium oxide content is 28wt%, iron oxide content is 50wt%, potash content is 5wt%, and content of magnesia is 1wt%, and dicalcium silicate, tricalcium silicate total content are 10wt%, cellulose powder content is 4.5wt%, and surplus is non-oxide cerium and the impurity different from adding material in rare earth.
Again above-mentioned compound is mixed with suitable quantity of water, put into kneader and fully mediate, then put into banded extruder obtain the bar shaped article shaped after extrusion.
At last the bar shaped article shaped is positioned over and is dried under air at room temperature that in article shaped, moisture volatilizees substantially, then after 120 minutes, can obtain dehydrogenation finished product E5 through shaping in calcining under 700 ℃.
Embodiment 6
At first cerium oxide, iron oxide, potash, magnesia, dicalcium silicate, tricalcium silicate, sodium carboxymethylcellulose and sesbania powder content in the rare earth that contains cerium oxide are measured, thereby can be according to the content of each raw material in compound in next step, need to determine the amount of rare earth and the amount that need to add each raw material in the rare earth.Obtain that in rare earth, cerium oxide content is 10wt%.
Next add potash, iron oxide, magnesia, dicalcium silicate, tricalcium silicate, sodium carboxymethylcellulose and sesbania powder in described rare earth, obtain compound and make in compound after fully mixing, cerium oxide content is 5wt%, iron oxide content is 45wt%, potash content is 15wt%, content of magnesia is 5wt%, dicalcium silicate, tricalcium silicate total content are 28.5wt%, sodium carboxymethylcellulose and sesbania powder total content are 1wt%, and surplus is non-oxide cerium and the impurity different from adding material in rare earth.
Again above-mentioned compound is mixed with suitable quantity of water, put into kneader and fully mediate, then put into banded extruder obtain the bar shaped article shaped after extrusion.
At last the bar shaped article shaped is positioned over and is dried under air at room temperature that in article shaped, moisture volatilizees substantially, then after 240 minutes, can obtain dehydrogenation finished product E6 through shaping in calcining under 600 ℃.
Embodiment 7
At first cerium oxide, iron oxide, potash, magnesium carbonate, dicalcium silicate, tricalcium silicate, carboxymethylcellulosodium sodium content in the rare earth that contains cerium oxide are measured, thereby can be according to the content of each raw material in compound in next step, need to determine the amount of rare earth and the amount that need to add each raw material in the rare earth.Obtain that in rare earth, cerium oxide content is 15wt%.
Next add potash, iron oxide, magnesium carbonate, dicalcium silicate, tricalcium silicate, sodium carboxymethylcellulose in described rare earth, obtain compound and make in compound after fully mixing, cerium oxide content is 8wt%, iron oxide content is 55wt%, potash content is 15wt%, and magnesium carbonate content is 10wt%, and dicalcium silicate, tricalcium silicate total content are 10wt%, carboxymethylcellulosodium sodium content is 1wt%, and surplus is non-oxide cerium and the impurity different from adding material in rare earth.
Again above-mentioned compound is mixed with suitable quantity of water, put into kneader and fully mediate, then put into banded extruder obtain the bar shaped article shaped after extrusion.
At last the bar shaped article shaped is positioned over and is dried under air at room temperature that in article shaped, moisture volatilizees substantially, then after 200 minutes, can obtain dehydrogenation finished product E7 through shaping in calcining under 700 ℃.
Comparative Examples 1
Cerous nitrate, potash, iron oxide, magnesia, dicalcium silicate, tricalcium silicate, sodium carboxymethylcellulose fully are mixed to get compound, in this compound, cerous nitrate content is 15wt%, iron oxide content is 50wt%, potash content is 15wt%, content of magnesia is 4wt%, and dicalcium silicate, tricalcium silicate total content are 15wt%, and carboxymethylcellulosodium sodium content is 1wt%.
Again above-mentioned compound is mixed with suitable quantity of water, put into kneader and fully mediate, then put into banded extruder obtain the bar shaped article shaped after extrusion.
At last the bar shaped article shaped is positioned over and is dried under air at room temperature that in article shaped, moisture volatilizees substantially, then after 120 minutes, can obtain dehydrogenation finished product C1 through shaping in calcining under 1000 ℃.
Evaluation Example
Dehydrogenation finished product E1-E6 and C1 that embodiment 1-6 and Comparative Examples 1 are prepared are used for the catalysis ethylbenzene dehydrogenation reaction, and to adopting conversion of ethylbenzene and selectivity of styrene after each catalyst to estimate.Wherein the appreciation condition of catalysis dehydrogenation activity is: the catalyst particles granularity is Φ 3.0 * (4-6) mm; Loaded catalyst 100ml; Ethylbenzene liquid air speed is 0.5-1.0hr
-1Water-oil factor (volume ratio) is 1.3; Reaction temperature is 570-640 ℃; Reaction pressure: normal pressure _-0.07MPa.Product is analyzed by gas chromatographicanalyzer.Wherein, ethylbenzene conversion ratio=(EB%-(EB%)) ÷ EB%; Selectivity of styrene=((SM%)-SM%) ÷ (EB%-(EB%)), in formula, (SM%) is cinnamic percentage composition in dehydrogenation liquid; SM% is cinnamic percentage composition in raw material; EB% is the percentage composition of ethylbenzene in raw material; (EB%) be the percentage composition of ethylbenzene in dehydrogenation liquid.The results are shown in Table 1.
By the data in table 1, can find out that the conversion of ethylbenzene of the dehydrogenation that the preparation method in employing the present invention obtains and selectivity of styrene all maintain an equal level mutually with the dehydrogenation that makes by conventional method.Experimental results show that and adopt the rare earth that contains cerium oxide directly can reach equally optionally purpose of high conversion rate of dehydrogenation, dehydrogenation as the raw material of preparation dehydrogenation.And the composition that may contain in rare earth such as silicates play the raw material that improves dehydrogenation intensity in the compound of calcium, magnesium, iron etc. and raw material consistent, addition that therefore can the corresponding raw material of corresponding minimizing; The compound of the potassium that may contain in rare earth simultaneously, can relatively reduce the addition of potassium compound this moment; Remaining impurity is generally the compound of rare earth element, a small amount of transition elements etc., shows that by experiment the existence of these impurity does not affect the catalysis dehydrogenation performance of dehydrogenation finished product.
Table 1
| The dehydrogenation finished product | Conversion of ethylbenzene % | Selectivity of styrene |
| E1 | 63.5 | 94.5 |
| E2 | 63.0 | 94.2 |
| E3 | 61.5 | 94.4 |
| E4 | 60.9 | 94.1 |
| E5 | 62.1 | 94.2 |
| E6 | 62.3 | 94.3 |
| E7 | 62.8 | 94.5 |
| C1 | 63.3 | 94.5 |
Obviously, above-described embodiment is only for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still belong among the protection domain of claim of the present invention.
Claims (8)
1. the preparation method of a dehydrogenation, comprise the steps:
(a) content of special component in the rare earth that contains cerium oxide is measured; In described rare earth, cerium oxide content is 5-35wt%;
(b) add iron oxide and/or iron oxide predecessor in the described rare earth that contains cerium oxide, potassium oxide and/or potassium oxide predecessor, calsil, pore creating material, mix rear formation compound, in described compound, described cerium oxide content is 1-30wt%, described iron oxide and/or iron oxide precursor amounts are 40-80wt%, described potassium oxide and/or potassium oxide precursor amounts are 5-25wt%, described calsil content is 10-30wt%, described Content of Pore-forming Agents is 1-5wt%, also add magnesia and/or magnesia predecessor, its content 1-10wt% in described mixture, surplus is impurity,
(c) described compound is mixed with suitable quantity of water, fully mediate, then obtain article shaped after extrusion;
(d) the first drying of described article shaped, then obtain described dehydrogenation finished product after calcining;
Wherein, the described special component that needs in step (a) to measure be in described rare earth cerium oxide and with add the identical compound of material described in step (b).
2. the preparation method of a kind of dehydrogenation according to claim 1, it is characterized in that: in step (b), cerium oxide content described in described compound is 10-20wt%, and described iron oxide and/or iron oxide precursor amounts are 60-70wt%.
3. the preparation method of a kind of dehydrogenation according to claim 1, it is characterized in that: in described rare earth, cerium oxide content is 15-20wt%.
4. the preparation method of a kind of dehydrogenation according to claim 1, it is characterized in that: in step (b), described pore creating material is one or more in sodium carboxymethylcellulose, sesbania powder, cellulose powder.
5. the preparation method of a kind of dehydrogenation according to claim 1, it is characterized in that: in step (b), described potassium oxide predecessor is potash and/or saleratus.
6. the preparation method of a kind of dehydrogenation according to claim 1, it is characterized in that: in step (d), described calcination temperature is 500-1000 ℃, and described calcination time is 5-250 minute.
7. the preparation method of a kind of dehydrogenation according to claim 6, it is characterized in that: in step (d), described calcining heat is 600-800 ℃.
8. the preparation method of a kind of dehydrogenation according to claim 1, is characterized in that: in step (d), also comprise the shaping process after described calcining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810119051.0A CN101658790B (en) | 2008-08-28 | 2008-08-28 | Method for preparing dehydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810119051.0A CN101658790B (en) | 2008-08-28 | 2008-08-28 | Method for preparing dehydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101658790A CN101658790A (en) | 2010-03-03 |
| CN101658790B true CN101658790B (en) | 2013-06-12 |
Family
ID=41787165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810119051.0A Active CN101658790B (en) | 2008-08-28 | 2008-08-28 | Method for preparing dehydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101658790B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233844A (en) * | 2015-11-13 | 2016-01-13 | 无锡清杨机械制造有限公司 | Preparation method of catalyst for preparing propene through propane dehydrogenation |
| CN108722430A (en) * | 2018-04-19 | 2018-11-02 | 天津理工大学 | Using nano-sized iron oxide as catalyst for phenylethylene dehydrogenation of source of iron and preparation method thereof |
| CN111995882A (en) * | 2020-08-04 | 2020-11-27 | 内蒙古工业大学 | Porous calcium silicate rare earth ion-loaded filler powder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230461A (en) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | Alkyl arene dehydrogenating catalyst |
| CN1443735A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Method for preparing alkyl aromatics dehydrogenation catalyst |
| CN1549851A (en) * | 2001-07-18 | 2004-11-24 | ���з����о���˾ | Hydrogenation and dehydrogenation processes and catalysts therefor |
-
2008
- 2008-08-28 CN CN200810119051.0A patent/CN101658790B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230461A (en) * | 1998-03-30 | 1999-10-06 | 中国石油化工总公司 | Alkyl arene dehydrogenating catalyst |
| CN1549851A (en) * | 2001-07-18 | 2004-11-24 | ���з����о���˾ | Hydrogenation and dehydrogenation processes and catalysts therefor |
| CN1443735A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Method for preparing alkyl aromatics dehydrogenation catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 廖仕杰等.焙烧温度对乙苯脱氢催化剂Fe2O3-K2O性能的影响.《催化学报》.2008,第29卷(第6期),583-587. * |
| 祝以湘等.乙苯脱氢催化剂的开发.《石油化》.1998,第27卷204-208. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101658790A (en) | 2010-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2160702C (en) | Dehydrogenation catalyst having improved moisture stability, and process for making and using the catalyst | |
| CN103127939B (en) | Cellular integral sulfur-tolerant methanation catalyst and preparation method thereof | |
| CN101658790B (en) | Method for preparing dehydrogenation catalyst | |
| CN102335546A (en) | Preparation method of normal temperature iron oxide desulfurizing agent | |
| CN103864644A (en) | Method for preparing cyanobenzene by ammonifying benzoic acid gaseous phase | |
| CN104248961A (en) | Sulfur-tolerant shift catalyst and preparation method thereof | |
| CN101992092B (en) | Catalyst for preparing styrene by dehydrogenizing ethylbenzene and preparation method thereof | |
| CN101279263B (en) | Catalyst for preparation of styrene by ethylbenzene dehydrogenation | |
| CN106582693B (en) | Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof | |
| CN103769204A (en) | Catalyst used for production of isobutene via isomerization of n-butene skeleton, and preparation method and applications thereof | |
| CN103769141B (en) | Catalyst for phenylethylene dehydrogenation, preparation method and its usage | |
| CN107790148A (en) | Catalyst of diethylbenzene dehydrogenation divinylbenzene and its preparation method and application | |
| CN101822988B (en) | Method for preparing dehydrogenation catalyst for alkyl aromatics | |
| CN109569638A (en) | Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof | |
| CN105478132B (en) | Catalyst for phenylethylene dehydrogenation of low-carbon type and its preparation method and application | |
| CN110681391A (en) | Low-water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof | |
| CN102040465A (en) | Method for preparing styrene by dehydrogenation of ethylbenzene | |
| CN105617853A (en) | Gaseous phase dechlorinating agent and preparation method thereof | |
| CN107790149A (en) | Diethylbenzene dehydrogenation and preparation method thereof | |
| CN102350350A (en) | Catalysts used in production of promoter 2,2'-dithiobisbenzothiazole, and preparation method thereof | |
| CN101157036A (en) | A low-grade alkalization hydrocarbons water vapour conversion catalyst and its preparing method | |
| CN106582685A (en) | Low-temperature ethylbenzene dehydrogenation catalyst and preparing method thereof | |
| CN104815688B (en) | Iron-based molecular sieve catalyst and preparation method and application thereof | |
| CN101148389A (en) | Method for preparing styrene by ethylbenzene dehydrogenation | |
| CN105562025B (en) | Low temperature ethylbenzene dehydrogenation catalyst with low water ratio and its preparation method and application |
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 | ||
| CP03 | Change of name, title or address |
Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Patentee after: SUZHOU HENGSHENG NEW MATERIAL Co.,Ltd. Patentee after: SHANGHAI JIAO TONG University Address before: 100080, Beijing, Haidian District people's Congress Road 33, the big line foundation building 9 floor Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. Patentee before: SUZHOU HENGSHENG NEW MATERIAL Co.,Ltd. Patentee before: SHANGHAI JIAO TONG University |
|
| CP03 | Change of name, title or address |