KR19980069072A - Method for producing aluminophosphate having high pore characteristics - Google Patents
Method for producing aluminophosphate having high pore characteristics Download PDFInfo
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- KR19980069072A KR19980069072A KR1019970005957A KR19970005957A KR19980069072A KR 19980069072 A KR19980069072 A KR 19980069072A KR 1019970005957 A KR1019970005957 A KR 1019970005957A KR 19970005957 A KR19970005957 A KR 19970005957A KR 19980069072 A KR19980069072 A KR 19980069072A
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- aluminophosphate
- acidic
- aluminum salt
- aluminum
- alkali
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- 239000011148 porous material Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000002378 acidificating effect Effects 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 239000002245 particle Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract description 3
- 238000002407 reforming Methods 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 7
- 239000000017 hydrogel Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- -1 propargyl alcohols Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
본 발명은 정유 및 석유화학 산업에서 개질촉매, 수첨촉매 및 수소-탈수소화촉매 등의 촉매용 담체로 사용할 수 있는 알루미노포스페이트의 제조방법에 관한 것으로, 더욱 상세하게는 인이 함유된 산성 알루미늄염과 알카리알루미늄염을 중화시켜 수첨촉매 담체로 사용되는 알루미노포스페이트를 제조하는 방법에 있어서, 침전된 알루미노포스페이트 속의 미세입자의 숙성시 산성 수용액 또는 인을 함유하는 산성 알루미늄염과 암모니아 또는 수용성인 알카리알루미늄염을 이용하여 pH 2 내지 6.5의 산성영역과 pH 8 내지 12의 알카리 영역 사이에서 2회 이상, 바람직하게는 2회 내지 10회로 반복하여 반응 및 숙성시킴으로 보다 균일하고 큰 입자를 얻고 입자의 응집체의 성장을 촉진시켜 높은 기공량과 큰 기공경을 갖는 알루미노포스페이트를 제조하는 방법인 것이다.The present invention relates to a method for preparing aluminophosphate that can be used as a catalyst carrier for reforming catalysts, hydrogenation catalysts, and hydrogen-dehydrogenation catalysts in the oil and petrochemical industries, and more particularly, acidic aluminum salts containing phosphorus. In the method for producing aluminophosphate used as a hydrocatalyst carrier by neutralizing the alkali aluminum salt, the acidic aluminum salt containing acidic aqueous solution or phosphorus and the ammonia or water-soluble alkali when the fine particles in the precipitated aluminophosphate are aged By using the aluminum salt, the reaction and aging are repeated two or more times, preferably two to ten times, between an acidic region of pH 2 to 6.5 and an alkaline region of pH 8 to 12 to obtain more uniform and large particles and aggregate of particles. Promotes growth of the aluminophosphate having high pore amount and large pore diameter It will be entity.
본 발명에 따라 침전된 알루미노포스페이트를 산성영역과 알카리영역에서 각각 반복적으로 반응시키고 숙성시킴으로서 정유 및 석유화학 산업에서 수첨촉매용 담체로서 적합한 높은 기공량과 큰 평균 기공경을 갖는 알루미노포스페이트를 제조할 수 있다.Aluminophosphate having a high pore amount and a large average pore size suitable as a carrier for hydrogenation catalysts in the oil and petrochemical industry is prepared by repeatedly reacting and aging the aluminophosphate precipitated in the acidic and alkaline regions, respectively. can do.
Description
본 발명은 정유 및 석유화학 산업에서 개질촉매, 수첨촉매 및 수소-탈수소화촉매 등의 촉매용 담체로 사용할 수 있는 알루미노포스페이트의 제조방법에 관한 것으로, 더욱 상세하게는 수첨촉매 담체로 적합한 높은 기공량과 큰 기공경을 갖는 알루미노포스페이트를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing aluminophosphate that can be used as a catalyst carrier for reforming catalysts, hydrogenation catalysts, and hydrogen-dehydrogenation catalysts in the oil and petrochemical industry, and more particularly, high porosity suitable as a hydrogenation catalyst carrier. The present invention relates to a method for producing aluminophosphate having an amount and a large pore diameter.
알루미노포스페이트는 오래 전부터 다양한 촉매용 담체로 그 이용가능성에 대해 논의되어 왔으며 수첨 촉매 및 프로파길 알코올의 액상 탈수소화 반응에서 높은 활성을 나타낸다고 알려져 있다[미국특허 제4717704호, 미국특허 제4717705호, 미국특허 제4839028호, 미국특허 제5001101호, J. Phys. Chem. 81(16) 1583(1977)].Aluminophosphates have long been discussed for their applicability as carriers for various catalysts and are known to exhibit high activity in the liquid phase dehydrogenation of hydrogenated catalysts and propargyl alcohols [US Pat. No. 4477704, US Pat. U.S. Patent No. 4839028, U.S. Patent No. 5001101, J. Phys. Chem. 81 (16) 1583 (1977).
알루미노포스페이트는 알루미늄 이온과 인산 이온의 중화반응에서 인과 알루미늄의 몰비가 화학양론치보다 작을 경우에 얻어지며 순수한 알루미나와 인산 알루미늄과는 다른 특성을 보이는 것으로 알려져 있다.Aluminophosphate is obtained when the molar ratio of phosphorus and aluminum is lower than stoichiometry in the neutralization reaction of aluminum ions and phosphate ions, and is known to show different properties from pure alumina and aluminum phosphate.
미국특허 제4717704호와 제4717705호, 미국특허 제4839028호 및 미국특허 제5001101호에는 알루미노포스페이트를 이용한 수첨촉매 제조방법이 기술되어 있는데 그 제조방법은 다음과 같다. 먼저 산성 알루미늄염 수용액과 인과 알루미늄의 몰비가 0.06 내지 0.30에 해당하는 인화합물을 혼합한 혼합수용액을 수용성인 알카리알루미늄염으로 중화적정시켜 20 내지 90℃의 온도, 5.5 내지 10.0의 pH에서 1차 숙성한 후, 알카리알루미늄염으로 pH를 조절하여 pH 8 내지 12, 20 내지 90℃의 온도에서 0.1 내지 10시간 2차 숙성하여 알루미노포스페이트 침전을 얻는다. 침전된 알루미노포스페이트는 물로 수세하여 불필요한 염들을 제거하고 탈수과정을 거쳐 최종 알루미노포스페이트 수화겔을 제조한다. 제조된 수화겔은 촉매 성분과 혼합하여 성형, 건조 및 열처리하여 최종 수첨촉매를 제조한다.U.S. Pat. Nos. 471704704 and 471705705, U.S. Pat. No. 48,39028, and U.S. Pat.No. 500,1101 describe the preparation of a hydrogenated catalyst using aluminophosphate. First, the mixed aqueous solution containing the aqueous solution of acidic aluminum salt and the phosphorus compound having a molar ratio of phosphorus and aluminum is 0.06 to 0.30. After that, the pH is adjusted with an alkali aluminum salt, followed by secondary aging at a temperature of pH 8-12, 20-90 ° C. for 0.1-10 hours to obtain aluminophosphate precipitate. The precipitated aluminophosphate is washed with water to remove unnecessary salts and dehydrated to prepare the final aluminophosphate hydrogel. The prepared hydrogel is mixed with the catalyst component to be molded, dried and heat treated to produce a final hydrogenated catalyst.
이러한 종래의 기술로 제조된 촉매의 경우, 300m2/g의 높은 비표면적과 70Å보다 작은 직경을 갖는 기공이 전체 기공량의 80%를 넘는 기공 특성을 갖게 된다. 하지만 이렇게 제조된 촉매는 니켈, 바나듐, 알카리 금속 등의 거대 금속 화합물을 포함하지 않은 경유와 같은 경질유의 경우에는 높은 반응 활성을 보이지만, 이러한 금속 화합물이 많이 함유되어 있는 잔사유와 같은 중질유의 경우에는 이들 금속 화합물이 촉매 표면에 침적되거나 세공입구를 막아 유효반응활성점을 감소시켜 전체 촉매반응활성을 감소시키게 됨에 따라 보다 높은 기공량과 큰 기공경을 갖는 새로운 알루미노포스페이트 담체가 요구된다.In the case of the catalyst prepared according to the prior art, pores having a high specific surface area of 300 m 2 / g and a diameter of less than 70 mm 3 have pore characteristics exceeding 80% of the total pore amount. However, the catalyst prepared in this way shows high reaction activity in light oils such as light oils that do not contain macrometal compounds such as nickel, vanadium, and alkali metals, but in the case of heavy oils such as residues containing many of these metal compounds. As these metal compounds are deposited on the surface of the catalyst or block the pore inlet, the effective reaction activity point is reduced, thereby reducing the overall catalytic reaction activity. Therefore, a new aluminophosphate carrier having a higher pore amount and a larger pore diameter is required.
높은 기공량과 큰 기공경을 갖는 알루미노포스페이트를 제조하기 위한 가장 효율적인 방법은 생성입자의 고유특성과 응집체의 크기 및 응집모양을 변화시키는 것이다. 예를 들면 크고 불균일한 입자들은 느슨하게 응집되어 큰 기공경의 알루미노포스페이트를 제조할 수 있지만 불규칙한 응집으로 인해 세공의 부포가 불균일하고 반응에 직접 관여하지 못하는 거대기공의 형성을 초래할 수 있다. 반대로 작은 입자들로 응집된 경우 미세한 입자들이 침전된 알루미노포스페이트의 기공을 채워 전체적인 기공량을 감소시킬 뿐만 아니라 생성된 기공의 크기도 작아 그 활용 영역이 제한되게 된다.The most efficient method for producing aluminophosphate having high pore amount and large pore diameter is to change the intrinsic properties of the particles produced, the size and the shape of the aggregates. For example, large and non-uniform particles can loosely aggregate to produce aluminophosphates with large pore diameters, but irregular aggregation can result in the formation of macropores that are uneven in pores and do not directly participate in the reaction. On the contrary, when aggregated into small particles, the fine particles fill the pores of the precipitated aluminophosphate to reduce the overall pore amount, and the size of the generated pores is small, thereby limiting the utilization area.
본 발명자들은 상기한 바와 같은 종래 기술의 문제점을 해결하기 위하여 예의 연구한 결과, 침전된 알루미노포스페이트 속의 미세입자의 숙성시 산성 수용액 또는 인을 함유하는 산성 알루미늄과 암모니아 또는 수용성인 알카리알루미늄염을 이용하여 pH 2 내지 6.5의 산성영역과 pH 8 내지 12의 알카리영역 사이에서 2회 이상, 바람직하게는 2회 내지 10회로 반복하여 반응 및 숙성시킴으로써 보다 균일하고 큰 입자를 얻고 입자의 응집체의 성장을 촉진시켜 높은 기공량과 큰 기공경을 갖는 알루미노포스페이트를 제조할 수 있다는 것을 알게 되어 본 발명에 이르게 되었다.The present inventors have diligently studied to solve the problems of the prior art as described above, and as a result of the aging of the fine particles in the precipitated aluminophosphate, the acidic aqueous solution or phosphorus containing acid aluminum and ammonia or water-soluble alkali aluminum salt By reacting and aging two or more times, preferably two to ten times, between an acidic region of pH 2 to 6.5 and an alkaline region of pH 8 to 12 to obtain more uniform and large particles and to promote the growth of aggregates of particles. It has been found that the aluminophosphate having a high pore amount and a large pore diameter can be produced, thereby leading to the present invention.
이에 본 발명은 정유 및 석유화학 산업에서 수첨촉매용 담체로서 적합한 높은 기공량과 큰 기공량을 갖는 알루미노포스페이트를 제조하는 방법을 제공하는데 그 목적이 있는 것이다.Accordingly, an object of the present invention is to provide a method for producing aluminophosphate having a high pore amount and a large pore amount suitable as a carrier for a hydrogenation catalyst in the oil refining and petrochemical industries.
본 발명은 인이 함유된 산성알루미늄염과 알카리알루미늄염을 중화시켜 알루미노포스페이트를 제조하는 방법에 있어서, 인산과 같은 산성인 인산염을 함유하는 산성알루미늄염 수용액과 암모니아 또는 알카리금속인산염을 포함하는 알카리알루미늄염 및 알카리알루미늄염 수용액을 20 내지 90℃에서 중화적정 또는 침전시키고 20 내지 90℃, pH 8 내지 12의 조건에서 5분 내지 60분간 숙성시킨 후, 산성 수용액 또는 인을 함유하는 산성알루미늄염과 암모니아 또는 수용성인 알카리알루미늄염을 이용하여 pH를 2 내지 6.5의 산성영역과 8 내지 12의 알카리영역으로 변화시켜 2회 이상, 바람직하게는 2회 내지 10회로 반복적으로 반응과 숙성을 시킨 후, 최종적으로 20 내지 90℃, pH 8 내지 12의 조건에서 5분 내지 720분간 숙성시켜서, 제조된 알루미노포스페이트를 탈수, 건조 및 열처리하여 높은 기공량과 큰 기공경을 갖는 알루미노포스페이트를 제조하는 방법인 것이다.The present invention provides a method for producing aluminophosphate by neutralizing phosphoric acid and alkaline aluminum salts, the alkali comprising an aqueous solution of acidic aluminum salt containing an acidic phosphate such as phosphoric acid and ammonia or alkali metal phosphate Neutralization titration or precipitation of the aqueous aluminum salt and alkaline aluminum salt solution at 20 to 90 ℃ and aged for 5 minutes to 60 minutes at the conditions of 20 to 90 ℃, pH 8 to 12, and then the acidic aluminum salt or acidic aluminum salt containing phosphorus and After changing the pH to an acidic region of 2 to 6.5 and an alkaline region of 8 to 12 using ammonia or a water-soluble alkali aluminum salt, the reaction and aging are repeated twice or more, preferably 2 to 10 times, and finally 5 to 720 minutes at 20 to 90 ℃, pH 8 to 12 conditions, the prepared aluminophosphate Water, then dried and heat-treated to a method for producing the alumino-phosphates having a high pore volume and large pore diameter.
이하 본 발명을 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 인산과 같은 산성인 인산염을 함유하는 산성알루미늄염 수용액과 암모니아 또는 알카리금속 인산염을 포함하는 알카리알루미늄염 및 알카리알루미늄염 수용액을 20 내지 90℃에서 중화 적정 또는 침전시킨 후 20 내지 90℃, pH 8 내지 12의 조건에서 5분 내지 60분간 숙성시켜 알루미노포스페이트를 제조한다. 이때 첨가된 인의 함량은 인가 알루미늄의 몰비로 0.05 내지 0.4이다.In the present invention, 20 to 90 ℃ after neutralizing titration or precipitation of an aqueous solution of acid aluminum salt containing an acidic phosphate such as phosphoric acid and an aqueous solution of alkaline aluminum and alkali aluminum salt containing ammonia or alkali metal phosphate at 20 to 90 ℃, Aluminophosphate is prepared by aging at a pH of 8 to 12 for 5 to 60 minutes. At this time, the content of phosphorus added is 0.05 to 0.4 in the molar ratio of the applied aluminum.
제조된 알루미노포스페이트는 다시 인산, 질산, 염산, 황산 또는 이들의 혼합용액과 인산염을 함유하는 산성알루미늄염 또는 산성알루미늄염 수용액으로 pH를 2 내지 6.5로 조절하여 5분에서 60분간 반응시킨다. 여기서 사용된 인산염을 함유하는 산성알루미늄염 또는 산성알루미늄염 수용액에 포함된 인의 함량은 초기에 첨가된 인과 알루미늄의 몰비와 동일하게 하는 것이 좋다.The prepared aluminophosphate is reacted with an acidic aluminum salt or an acidic aluminum salt aqueous solution containing phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, or a mixed solution thereof and phosphate, and then the pH is adjusted to 2 to 6.5 for 5 minutes to 60 minutes. The content of phosphorus in the acidic aluminum salt or acidic aluminum salt solution containing phosphate used herein is preferably equal to the molar ratio of phosphorus and aluminum added initially.
반응 후 생성된 비정질의 미세한 알루미노포스페이트는 쉽게 용해되어 이미 결정화된 입자 표면에 부착하게 된다. 여기에 다시 암모니아 또는 인이 첨가된 알카리금속 인산염을 포함하는 알카리알루미늄염 및 알카리알루미늄염 수용액을 첨가하고 20 내지 90℃, pH 8 내지 12의 조건에서 5분 내지 60분간 숙성시킴으로서 입자가 좀 더 결정화되고, 여기에 부착된 비정질의 미세한 알루미노포스페이트의 결정화가 진행되어 보다 크고 균일한 입자 및 입자의 응집체로 성장하게 된다. 이러한 과정을 2회 이상 반복함으로서 보다 큰 입자가 형성되어 높은 기공량과 큰 기공경을 갖는 알루미노포스페이트를 제조할 수 있다.The amorphous fine aluminophosphate produced after the reaction is easily dissolved and adheres to the surface of the already crystallized particles. The particles are further crystallized by adding an alkali aluminum salt and an alkali aluminum salt aqueous solution containing an alkali metal phosphate to which ammonia or phosphorus is added again, and aging at 20 to 90 ° C. and pH 8 to 12 for 5 minutes to 60 minutes. As a result, the crystallization of the amorphous fine aluminophosphate adhering thereto is advanced to grow into larger and more uniform particles and aggregates of particles. By repeating this process two or more times, larger particles may be formed to prepare aluminophosphates having high pore amounts and large pore diameters.
상기 과정은 2회 내지 10회 반복하는 것이 바람직하며 보다 경제적이다. 또한 최종적으로 실시하는 숙성은 20 내지 90℃, pH 8 내지 12의 조건에서 5분 내지 720분간, 바람직하게는 5분 내지 120분간 숙성시킨다.The process is preferably repeated 2 to 10 times and is more economical. In addition, the final aging is carried out for 5 to 720 minutes, preferably 5 to 120 minutes under the conditions of 20 to 90 ℃, pH 8 to 12.
제조된 알루미노포스페이트는 물로 충분히 수세한 뒤 진공뷰너깔대기 또는 원심분리기를 이용하여 탈수시킨다. 탈수과정을 거친 알루미노포스페이트 수화겔은 30 내지 150℃, 바람직하게는 80 내지 120℃의 온도에서 완전히 건조시키고 공기 분위기에서 450 내지 900℃, 바람직하게는 500 내지 650℃에서 열처리하여 높은 기공량과 큰 기공경을 갖는 알루미노포스페이트를 제조한다.The prepared aluminophosphate is washed with water sufficiently and dewatered using a vacuum burr funnel or centrifuge. The dehydrated aluminophosphate hydrogel is completely dried at a temperature of 30 to 150 ° C., preferably 80 to 120 ° C., and heat-treated at 450 to 900 ° C., preferably 500 to 650 ° C. in an air atmosphere to obtain high pore volume and large An aluminophosphate having a pore diameter is prepared.
제조된 알루미노포스페이트는 150 내지 450m2/g의 비표면적, 0.5 내지 3.0cc/g의 기공량 및 50 내지 500Å의 평균 기공경을 갖게 된다.The prepared aluminophosphate has a specific surface area of 150 to 450 m 2 / g, a pore amount of 0.5 to 3.0 cc / g and an average pore diameter of 50 to 500 kPa.
일반적으로 생성된 침전물에는 결정화가 잘 발달된 입자와 그렇지 못한 입자가 불균일하게 존재하게 된다. 이런 경우에 제조된 알루미노포스페이트의 기공량이 감소하며 기공 분포가 불균일하게 된다. 본 발명에서는 침전후 숙성시켜 제조한 알루미노포스페이트를 pH 2 내지 6.5의 산성영역과 8 내지 12의 알카리 영역으로 변화시켜 2회 이상 반복적으로 반응과 숙성을 시킴으로 인해 초기에 생성된 비정질의 알루미노포스페이트는 pH 2 내지 6.5의 산성 영역에서 다시 용해되어 보다 결정화가 잘 진행된 알루미노포스페이트 표면에 부착되고 이것을 다시 인을 함유하는 알카리알루미늄염으로 pH 8 내지 12의 알카리 영역에서 다시 숙성시킬 경우 결정화 반응이 진행되어 보다 균일하고 큰 입자 및 입자의 응집체를 얻게 된다. 이러한 반응과 숙성과정을 되풀이하면서 침전된 알루미노포스페이트는 보다 균일하고 큰 입자 및 입자의 응집체로 성장하여 높은 기공량과 큰 기공경을 갖는 알루미노포스페이트가 제조된다.In general, the resultant precipitate is a non-uniform presence of particles well-developed crystallization. In this case, the amount of porosity of the prepared aluminophosphate decreases and the pore distribution becomes nonuniform. In the present invention, the amorphous aluminophosphate initially produced by changing the aluminophosphate prepared by precipitation into an acidic region of pH 2 to 6.5 and an alkaline region of 8 to 12 and repeatedly reacting and ripening two or more times Is re-dissolved in the acidic region of pH 2 to 6.5 and attached to the surface of the aluminophosphate which is more well crystallized, and when it is aged again in the alkaline region of pH 8 to 12 with an alkali aluminum salt containing phosphorus again, the crystallization reaction proceeds. This results in more uniform and larger particles and aggregates of particles. The aluminophosphate precipitated while repeating this reaction and aging process is grown into more uniform and larger particles and aggregates of particles to prepare aluminophosphate having a high pore amount and a large pore diameter.
본 발명에서 사용되는 산성알루미늄염 수용액은 질화알루미늄, 염화알루미늄 또는 황화알루미늄과 같은 산성 알루미늄염을 증류수에 용해시켜 제조한다. 산성알루미늄염 수용액에서 첨가되는 인성분을 함유하는 인화합물은 인산과 포스포러스산이 사용될 수 있으며 가격과 편의성에서 인산을 사용하는 것이 바람직하다.The aqueous acidic aluminum salt solution used in the present invention is prepared by dissolving an acidic aluminum salt such as aluminum nitride, aluminum chloride or aluminum sulfide in distilled water. Phosphorous compounds containing phosphorus added in the aqueous acidic acid salt solution may be used phosphoric acid and phosphoric acid, and it is preferable to use phosphoric acid for cost and convenience.
또한 침전시 또는 알카리 영역으로 pH 조절시 사용되는 알카리알루미늄염은 알루미늄산나트륨을 사용할 수 있으며 알카리알루미늄염에 첨가되는 인화합물은 인산암모늄, 인산수소암모늄, 알카리금속인산염, 알카리금속수소암모늄 등이 사용될 수 있다.In addition, the alkali aluminum salt used for precipitation or pH adjustment to the alkaline region may use sodium aluminate. The phosphorus compound added to the alkali aluminum salt may be ammonium phosphate, ammonium hydrogen phosphate, alkali metal phosphate, or alkali metal ammonium hydrogen. Can be.
1회 알카리 영역에서 숙성한 알루미노포스페이트를 산성 영역으로 pH를 조절할 때에는 필요에 따라서는 산성알루미늄염 대신에 인산, 질산, 염산, 황산 또는 이들의 혼합 용액을 사용할 수 있다.When adjusting the pH of the aluminophosphate aged in the alkaline region to the acidic region, phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid or a mixed solution thereof may be used in place of the acidic aluminum salt, if necessary.
이하 본 발명을 실시예에 의거하여 더욱 상세하게 설명하면 다음과 같으며, 본 발명은 다음의 실시예에 국한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the following Examples.
[실시예]EXAMPLE
실시예 1Example 1
질화알루미늄 375g과 85% 인산 11.5g을 5ℓ 비이커에 넣고 증류수 800ml에 녹여 질화알루미늄수용액을 제조한 후 이 수용액을 50℃로 가열하였다(단계 A). 제조된 질화알루미늄 수용액을 10중량% 암모니아 수용액을 이용하여 중화적정하였다(단계 B). 중화적정되어 침전된 알루미노포스페이트를 10중량% 암모니아 수용액을 이용하여 pH 9로 조절한 후 약 20분간 숙성시켰다(단계 C). 숙성 후 5중량% 질산 수용액을 이용하여 pH를 4로 조정하고 교반기로 강하게 약 20분간 반응시켰다(단계 D). 반응 후 다시 10중량% 암모니아 수용액으로 pH를 9로 조정하여 약 20분간 숙성시켰다(단계 E). 숙성후 다시 5중량% 질산 수용액을 이용하여 pH를 4로 조정하고 교반기로 강하게 약 20분간 반응시켰다(단계 F). 반응 후 다시 10중량% 암모니아 수용액으로 pH를 9로 조정하여 약 60분간 숙성시켰다(단계 G). 숙성이 끝난 침전물을 뷰너깔대기를 이용하여 증류수로 충분히 수세시켰다(단계 H). 수세된 알루미노포스페이트를 진공분위기에서 뷰너깔대기를 이용하여 탈수시켰다(단계 I). 탈수된 수화겔은 보통 80 내지 90%의 수분을 함유하고 있다. 얻어진 수화겔을 상압건조기에서 80℃에서 24시간 완전히 건조시킨 후 500℃에서 5시간 공기분위기에서 열처리하여 최종 알루미노포스페이트(담체 A)를 제조하였다(단계 J).375 g of aluminum nitride and 11.5 g of 85% phosphoric acid were added to a 5 L beaker, dissolved in 800 ml of distilled water to prepare an aqueous aluminum nitride solution, and the aqueous solution was heated to 50 ° C. (step A). The prepared aluminum nitride aqueous solution was neutralized with 10 wt% aqueous ammonia solution (step B). Neutralized titrated aluminophosphate was adjusted to pH 9 with a 10% by weight aqueous ammonia solution and aged for about 20 minutes (step C). After aging, the pH was adjusted to 4 using 5% by weight aqueous nitric acid solution and reacted strongly with a stirrer for about 20 minutes (step D). After the reaction, the pH was adjusted to 9 with 10% by weight aqueous ammonia solution and aged for about 20 minutes (step E). After aging, the pH was adjusted to 4 using 5 wt% aqueous nitric acid solution and reacted strongly with a stirrer for about 20 minutes (step F). After the reaction, the pH was adjusted to 9 with 10% by weight aqueous ammonia solution and aged for about 60 minutes (step G). The aged precipitate was washed with distilled water sufficiently using a Buchner funnel (step H). The washed aluminophosphate was dehydrated using a Buchner funnel in a vacuum atmosphere (Step I). Dehydrated hydrogels usually contain 80 to 90% moisture. The obtained hydrogel was completely dried in an atmospheric pressure dryer at 80 ° C. for 24 hours and then heat-treated at 500 ° C. for 5 hours in an air atmosphere to prepare a final aluminophosphate (carrier A) (step J).
실시예 1에 의해 제조된 알루미노포스페이트(담체 A)의 물리특성을 마이크로메트릭스 인스트루먼트 코포레이션사의 모델 ASAP 2400 V3.03의 질소흡착법에 의해 측정하였다.The physical properties of the aluminophosphate (carrier A) prepared in Example 1 were measured by nitrogen adsorption method of model ASAP 2400 V3.03 manufactured by Micrometrics Instruments Corporation.
표 1에 실시예 1에 의해 제조된 알루미노포스페이트의 기공 특성을 나타내었다.Table 1 shows the pore characteristics of the aluminophosphate prepared in Example 1.
실시예 2Example 2
실시예 1의 공정에서 단계 D와 단계 E를 2회 더 반복하여 알루미노 포스페이트를 제조하였다(담체 B).In the process of Example 1, step D and step E were repeated two more times to prepare alumino phosphate (carrier B).
실시예 3Example 3
질화알루미늄 375g과 85% 인산 11.5g을 5ℓ 비이커에 넣고 증류수 800ml에 녹여 질화알루미늄수용액을 제조한 후 이 수용액을 50℃로 가열하였다. 제조된 질화알루미늄수용액을 10중량% 암모니아 수용액을 이용하여 중화적정하였다. 중화적정되어 침전된 알루미노포스페이트를 10중량% 암모니아 수용액을 이용하여 pH 9로 조절한 후 약 20분간 숙성시켰다. 숙성 후 질화알루미늄과 인산의 혼합수용액(인산과 알루미늄의 몰비=0.1)을 이용하여 pH를 4로 조정하고 교반기로 강하게 약 20분간 반응시켰다. 반응 후 다시 10중량% 암모니아 수용액으로 pH를 9로 조정하여 약 20분간 숙성시켰다. 숙성 후 다시 질화알루미늄과 인산의 혼합 수용액을 이용하여 pH를 4로 조정하고 교반기로 강하게 약 20분간 반응시켰다. 반응 후 다시 10중량% 암모니아 수용액으로 pH를 9로 조정하여 약 60분간 숙성시켰다.375 g of aluminum nitride and 11.5 g of 85% phosphoric acid were added to a 5 L beaker, dissolved in 800 ml of distilled water to prepare an aqueous aluminum nitride solution, and the aqueous solution was heated to 50 ° C. The prepared aluminum nitride aqueous solution was neutralized titrated using a 10% by weight aqueous ammonia solution. Neutralized titrated aluminophosphate was adjusted to pH 9 using a 10% by weight aqueous ammonia solution and aged for about 20 minutes. After aging, the pH was adjusted to 4 using a mixed aqueous solution of aluminum nitride and phosphoric acid (molar ratio of phosphoric acid and aluminum = 0.1) and reacted strongly with a stirrer for about 20 minutes. After the reaction, the pH was adjusted to 9 with 10% by weight aqueous ammonia solution and aged for about 20 minutes. After aging, the pH was adjusted to 4 using a mixed aqueous solution of aluminum nitride and phosphoric acid and reacted strongly with a stirrer for about 20 minutes. After the reaction, the pH was adjusted to 9 with 10% by weight aqueous ammonia solution and aged for about 60 minutes.
이후의 공정은 실시예 1의 공정과 동일하게 실시하여(단계 H∼단계 J) 알루미노포스페이트를 제조하였다(담체 C).The subsequent steps were carried out in the same manner as in Example 1 (steps H to J) to prepare aluminophosphate (carrier C).
실시예 4Example 4
질화알루미늄 375g과 85% 인산 11.5g을 5ℓ 비이커에 넣고 증류수 800ml에 녹여 질화알루미늄수용액을 제조한 후 이 수용액을 50℃로 가열하였다. 제조된 질화알루미늄수용액을 10중량% 암모니아 수용액을 이용하여 중화적정하였다. 중화적정되어 침전된 알루미노포스페이트를 10중량% 암모니아 수용액을 이용하여 pH 9로 조절한 후 약 20분간 숙성시켰다. 숙성 후 5중량% 질산과 인산의 혼합 수용액을 이용하여 pH4를 조정하고 교반기로 강하게 약 20분간 반응시켰다. 반응 후 다시 10중량% 암모니아 수용액으로 pH를 9로 조정하여 약 20분간 숙성시켰다. 숙성 후 다시 5중량% 질산과 인산의 혼합 수용액을 이용하여 pH를 4로 조정하고 교반기로 강하게 약 20분간 반응시켰다. 반응 후 다시 10중량% 암모니아 수용액으로 pH를 9로 조정하여 약 60분간 숙성시켰다.375 g of aluminum nitride and 11.5 g of 85% phosphoric acid were added to a 5 L beaker, dissolved in 800 ml of distilled water to prepare an aqueous aluminum nitride solution, and the aqueous solution was heated to 50 ° C. The prepared aluminum nitride aqueous solution was neutralized titrated using a 10% by weight aqueous ammonia solution. Neutralized titrated aluminophosphate was adjusted to pH 9 using a 10% by weight aqueous ammonia solution and aged for about 20 minutes. After aging, pH 4 was adjusted using a mixed aqueous solution of 5% by weight nitric acid and phosphoric acid, and reacted strongly with a stirrer for about 20 minutes. After the reaction, the pH was adjusted to 9 with 10% by weight aqueous ammonia solution and aged for about 20 minutes. After aging, the pH was adjusted to 4 using a mixed aqueous solution of 5% by weight nitric acid and phosphoric acid and reacted strongly with a stirrer for about 20 minutes. After the reaction, the pH was adjusted to 9 with 10% by weight aqueous ammonia solution and aged for about 60 minutes.
이후의 공정은 실시예 1과 동일하게 실시하여(단계 H∼단계 J) 알루미노포스페이트를 제조하였다(담체 D).The subsequent steps were carried out in the same manner as in Example 1 (steps H to J) to prepare aluminophosphate (carrier D).
비교예 1Comparative Example 1
질화알루미늄 375g과 85% 인산 11.5g을 5ℓ 비이커에 넣고 증류수 800ml에 녹여 질화알루미늄수용액을 제조한 후 이 수용액을 50℃로 가열하였다. 제조된 질화알루미늄수용액을 10중량% 암모니아 수용액을 이용하여 중화적정하였다. 중화적정되어 침전된 알루미노포스페이트를 10중량% 암모니아 수용액을 이용하여 pH 9로 조절한 후 약 60분간 숙성시켰다. 숙성이 끝난 침전물을 뷰너깔대기를 이용하여 증류수로 충분히 수세시켰다. 수세된 알루미노포스페이트는 진공분위기에서 뷰너깔대기를 이용하여 탈수시켰다. 탈수된 수화겔은 보통 80 내지 90%의 수분을 함유하고 있다.375 g of aluminum nitride and 11.5 g of 85% phosphoric acid were added to a 5 L beaker, dissolved in 800 ml of distilled water to prepare an aqueous aluminum nitride solution, and the aqueous solution was heated to 50 ° C. The prepared aluminum nitride aqueous solution was neutralized titrated using a 10% by weight aqueous ammonia solution. The neutralized titrated precipitated aluminophosphate was adjusted to pH 9 using a 10% by weight aqueous ammonia solution and aged for about 60 minutes. The aged precipitate was washed with distilled water sufficiently using a Buchner funnel. The washed aluminophosphate was dehydrated using a Buchner funnel in a vacuum atmosphere. Dehydrated hydrogels usually contain 80 to 90% moisture.
얻어진 수화겔을 상압건조기에서 80℃에서 24시간 건조시켜 완전히 건조시킨 후 500℃에서 5시간 공기 분위기에서 열처리시켜 최종 알루미노포스페이트를 제조하였다(담체 E).The obtained hydrogel was dried in an atmospheric pressure dryer at 80 ° C. for 24 hours to be completely dried, and then heat-treated at 500 ° C. for 5 hours in an air atmosphere to prepare a final aluminophosphate (carrier E).
이상의 실시예와 비교예에 의해 제조된 담체의 특성을 표 1에 나타내었다.Table 1 shows the characteristics of the carrier prepared by the above Examples and Comparative Examples.
[표 1] 본 발명의 실시예 및 비교예에 의해 제조된 담체의 물리특성TABLE 1 Physical Properties of Carriers Prepared by Examples and Comparative Examples of the Present Invention
표 1에서 보는 바와 같이 본 발명에 의해 침전된 알루미노포스페이트를 산성영역과 알카리영역에서 각각 반복적으로 반응시키고 숙성시켜 제조한 알루미노포스페이트는 이러한 과정을 거치지 않은 담체 E의 시료에 비해 매우 높은 기공량과 큰 평균 기공경을 갖는 것을 알 수 있으며 반응과 숙성의 반복 횟수가 3회(담체 A)에서 5회(담체 B)로 증가함에 따라 총기공량과 평균기공경이 향상됨을 알 수 있다.As shown in Table 1, the aluminophosphate prepared by repeatedly reacting and aging the aluminophosphate precipitated by the present invention in the acidic region and the alkaline region, respectively, has a very high pore volume compared to the sample of the carrier E without this process. It can be seen that it has a large average pore diameter and the total pore volume and average pore diameter are improved as the number of repetitions of the reaction and ripening increases from three times (carrier A) to five times (carrier B).
본 발명에 따라 침전된 알루미노포스페이트를 산성영역과 알카리영역에서 각각 반복적으로 반응시키고 숙성시킴으로서 정유 및 석유화학 산업에서 수첨촉매용 담체로서 적합한 높은 기공량과 큰 평균 기공경을 갖는 알루미노포스페이트를 제조할 수 있다.Aluminophosphate having a high pore amount and a large average pore size suitable as a carrier for hydrogenation catalysts in the oil and petrochemical industry is prepared by repeatedly reacting and aging the aluminophosphate precipitated in the acidic and alkaline regions, respectively. can do.
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