CN1106373C - 制备甲醛的方法 - Google Patents
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 phosphor compound Chemical class 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 61
- 239000011574 phosphorus Substances 0.000 claims description 61
- 239000008246 gaseous mixture Substances 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 230000011218 segmentation Effects 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 239000002659 electrodeposit Substances 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 abstract 1
- 230000004913 activation Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000006887 Ullmann reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000003017 phosphorus Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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Abstract
一种通过甲醇氧化脱氢制备甲醛的方法，该方法包括将含如下组分a)0.1至50体积%甲醇，b)0.1至30体积%氧气，c)0至50体积%氧化氮，和d)0至60体积%水的气体混合物(i)在150至800℃下通过磷掺杂银催化剂固定床(a)，并对于每1cm2磷掺杂银催化剂固定床(a)横截面积以气体混合物(i)形式通过的每1kg甲醇，将0.01至100ppm(重量)的磷(按磷掺杂银催化剂固定床计)施于磷掺杂银催化剂固定床(a)上，所述磷为熔点或分解温度高于500℃的细分磷化合物形式(磷化合物P)。
Description
本发明涉及一种通过甲醇氧化脱氢制备甲醛的方法。
通过甲醇在由银晶体制备的催化剂固定床上氧化脱氢制备甲醛的方法一般是已知的(参见Ullmanns化学技术大全，第三版，Urban undSchwarzenberg，Munich/Berlin，1956，第7册，660-663页)。
从CN-A-85100530、DE-A-4022603和JP-A-38227/83已知，当在银催化剂存在下用磷化合物作为氧化甲醇制备甲醛的促进剂时，获得有利效果。
EP-A-0 467 169描述了通过在由银晶体层组成的催化剂固定床上甲醇氧化脱氢制备甲醛的方法，所述银晶体层包括粉末态含磷的盐作为促进剂。这种磷掺杂银催化剂固定床通过在甲醛制备开始前使其与磷化合物接触制备。
然而，这些方法还可以改进，因为催化剂在用于制备甲醛期间不断失去活性，这反映在收率降低上。因此，经过相当短时间后催化剂必须更换和再生。这样不得不中断甲醛制备过程。由于更换催化剂固定床和恢复甲醛制备过程的工艺耗时耗人力，因此方法的经济性取决于这种更换的频率。
本发明的一个目的是提供一种其中延长需要更换催化剂的时间的间隔方法。
我们已发现本发明目的可通过甲醇氧化脱氢制备甲醛的方法实现，该方法包括将含如下组分a)0.1至50体积％，优选10至40体积％甲醇，b)0.1至30体积％，优选5至20体积％氧气，c)0至50体积％，优选1至20体积％氧化氮，和d)0至60体积％，优选10至50体积％水的气体混合物(i)在150至800℃下通过磷掺杂银催化剂固定床(a)，并对于每1cm2磷掺杂银催化剂固定床(a)横截面积以气体混合物(i)形式通过的每1kg甲醇，将0.01至100ppm(重量)的磷(按磷掺杂银催化剂固定床计)施于磷掺杂银催化剂固定床(a)上，所述磷为熔点或分解温度高于500℃的细分磷化合物形式(磷化合物P)。
这些数据基于1巴压力。
该气体混合物一般含有0.25至0.60，优选0.35至0.50mol氧气/mol甲醇，0.2至3.0，优选0.67至1.75mol水/mol甲醇，和0.9至2.3，优选1.3至1.8mol氮气/mol甲醇。
适合本发明方法的磷掺杂银催化剂例如为通过如下方法获得的那些。I.安排通过由银盐水溶液电解淀积银获得的银晶体形成起始银催化剂固定床(a)，和II.在气体混合物(i)于150至800℃下通过固定床之前，使起始银催化剂固定床(a)与按银计1至20,000ppm(重量)的磷化合物(P)形式的磷接触。
步骤I描述的制备银晶体的方法通常是已知的(参见Ullmanns化学技术大全，第三版，Urban und Schwarzenberg，Munich/Berlin，1956，第7册，660-663页)。用DE-A-2322757中描述的起始催化剂固定床可获得特别好的结果。
特别当按照德国专利1166171中的描述进行电解时，可获得合适的银晶体。
作为电解质，使用硝酸银水溶液是优选的。这种硝酸银溶液通常具有pH1至4，并含有1至5wt％的银。pH有利地用硝酸调节。
使用的电极为电解银时惯用的那些。合适的阳极是已充有待氧化的银(通常为颗粒或粉末态)的袋子。合适的阴极特别为银片。
电解在电流密度80至500A/m2阴极面积和电解质温度10至30℃下有利地进行。
为获得这些电流密度，在大多数电解池中电压必须为1至15伏。
建议从阴极连续除去形成的银。通常获得颗粒尺寸0.2至5mm的银晶体。
一次电解通常足以获得适用的银晶体。
通常将最大平均直径0.2至10mm的银晶体排列形成包括一层或多层，优选1至9层银晶体层并具有床总厚度1至10cm的起始银催化剂固定床(a)。这种通常被称为“短床”的固定床通常是已知的(参见Ullmanns化学技术大全，第四版，Verlag Chemie，Weinheim-New York，第13册，539-541页)。
在第二步中，将起始银催化剂固定床(a)与按银计1至20,000ppm(重量)，优选5至5000ppm(重量)的磷接触，所述磷为熔点或分解温度高于500℃的细分磷化合物形式(磷化合物P)。
合适的磷化合物(P)为含磷的盐。这些磷化合物的例子为DE-A-4022603中提及的含磷盐，例如碱金属、碱土金属和重金属如Ag、Zn和Fe，或硼和铵的无机磷酸盐。
优选的是碱金属或碱土金属的磷酸盐或焦磷酸盐，如Na4P2O7、Li3PO4、Mg3(PO4)2、Ca3(PO4)2。
通常的工艺是将细粉末磷化合物(P)撒在银催化剂固定床上或用磷化合物(P)的溶液浸渍银催化剂固定床并将溶剂蒸发。
以粉末形式使用的磷化合物(P)的颗粒尺寸并不重要；通常为约1mm至约1μm。磷化合物(P)的溶液通常为含0.01至50wt％磷化合物(P)的水溶液。为浸渍银催化剂固定床，将其用这样一种溶液浸泡，或特别有利地，将溶液喷在要活化的银催化剂固定床上，然后将溶剂蒸发。
选取的喷在或撒在银催化剂固定床上的磷化合物(P)的用量应使磷的量为0.01至100，优选0.05至10mg/cm2磷掺杂银催化剂固定床横截面积。
按这种方式生产的银催化剂固定床(a)在开始通过气体混合物(i)时通常并不一开始就呈现其完全的催化剂活性。因此已发现在制备甲醛开始时活化磷掺杂银催化剂固定床(a)是有利的。
可通过就在开始通入气体混合物(i)之前将催化剂预热至300至400℃，和/或将预热至100至800℃，优选200至700℃的气体混合物(i)通过固定床，进行催化剂活化。在活化阶段开始时通过磷掺杂银催化剂固定床(a)的气体混合物(i)形式的甲醇的量，按每小时每cm2这种磷掺杂银催化剂固定床(a)的横截面积计，为0.001至1Kg，活化阶段通常需要0.1至100小时。在活化阶段将每单位时间通过磷掺杂银催化剂固定床(a)的气体混合物(i)的量连续增加至最终负荷值，通常为0.1至1kg。通常最迟在活化阶段结束时，不再需要气体混合物(i)的预热，原因是固定床被释放的反应热加热至所需的温度。
为使活化阶段和通过本发明方法制备甲醛相互连接而不中断，起始催化剂固定床(a)的活化有利地在(例如)惯用于甲醇氧化脱氢制备甲醛的固定床反应器中进行，同时气体混合物(i)连续通过该反应器。这里的反应器优选为立式的，气体混合物(i)由反应器顶部向下通过反应器。这些反应器和制备方法描述于(例如)EP-A-467 169、DE-A-2444586和EP-A-0150436中。
同样有利地选取反应器和起始银催化剂固定床的横截面积，使其相等，并将催化剂固定床放置于反应器中，以使银晶体层与气体混合物(i)的流动方向垂直。
磷掺杂银催化剂固定床(a)在活化阶段结束时具有最大活性，其活性在用于本发明方法期间慢慢且稳定地降低，这从甲醛收率降低上显而易见。
若按通过每cm2磷掺杂银催化剂固定床横截面积的每1kg气体混合物(i)形式的甲醇计，将0.01至100ppm(重量)的磷化合物(P)形式的磷(基于磷掺杂银催化剂固定床(a))，在优选不中断通入气体混合物(i)下连续或间断(在每一情况下以每通入限定量的气体混合物(i)后加入一部分方式)施于银催化剂固定床上，则可部分避免这种磷掺杂银催化剂固定床(a)的活性损失。对于连续施加，可减慢活性损失；对于分步间断施加，可部分抵消活性损失。
若后面施加磷化合物(P)间断进行，则选取的施加磷化合物(P)到磷掺杂银催化剂固定床上的间隔应使在该间隔期间，不多于500kg，优选1至5kg气体混合物(i)形式的甲醇(按1cm2磷掺杂银催化剂固定床横截面积计)通过催化剂固定床，因为要不然在此期间收率降低太多。
此外，用本发明催化剂固定床由甲醇氧化脱氢制备甲醛的方法按本身已知的方式，通过在500至750℃，特别是600至710℃下将气体混合物(i)通过磷掺杂银催化剂固定床进行。该方法通常在压力0.5至2巴，优选0.8至1.8巴下连续进行。这里有利的是，在短时间内将离开催化剂段的反应气体冷却至(例如)50-350℃。
优选磷掺杂银催化剂固定床位于立式反应器中，同时气体混合物(i)由顶部向下通过反应器。有利的是，选取的反应器与起始银催化剂固定床(b)的横截面积相等，并且催化剂固定床这样排列于反应器中，以使银晶体层与气体混合物(i)的流动方向垂直。
然后将冷却的气体混合物有利地送入吸收塔中，在该吸收塔中用水或甲醛/尿素水溶液从气体混合物中洗出甲醛。
还可在本发明方法中使用的通常已知的制备甲醛方法的各种有利变化描述于DE-A-2444586、DE-A-2451990、EP-A-0083427和EP-A-0150436中。
本发明方法能够特别经济地制备甲醛的事实是显而易见的，因为在本发明方法中甲醇氧化脱氢的收率和选择性在长时间内都特别高。
实施例1
在内径15cm的立式实验反应器中，安装具有相同直径的三层起始银催化剂固定床总床厚为2cm。下层由1000g颗粒尺寸1至2.5mm的银晶体组成，中间层由65g颗粒尺寸0.75至1mm的银晶体组成，上层由185g颗粒尺寸0.2至0.75mm的银晶体组成。
将粉末Na4P2O7形式的磷以1.3mg磷(按元素磷计算)/cm2固定床横截面积的量撒在起始银催化剂固定床表面上。将如此生产的磷掺杂银催化剂固定床加热至360℃。然后将包括甲醇、空气和水的气体混合物通过催化剂以使催化剂活化。在28小时活化期间，混合物量增加至32kg甲醇、21.4kg水和54kg空气/小时(最终进料)。活化阶段结束时固定床中的温度为700℃。这一进料流在整个实验期间保持不变。
在反应器连续操作期间，在表1中给出的操作时间之后再将一定量的粉末Na4P2O7形式的磷施于磷掺杂银催化剂固定床上(操作0天是指紧接在催化剂活化之后的时间点)。表1中给出相应量(累积量)。表1
| 操作天数 | 磷量[g/cm2] | 收率[％] |
| 0 | 1.3 | 90.1 |
| 4 | 1.3 | 89.7 |
| 6 | 1.42 | 90.1 |
| 9 | 1.42 | 89.6 |
| 11 | 1.61 | 90.0 |
| 16 | 1.61 | 89.3 |
| 17 | 1.70 | 89.9 |
Claims (4)
1.一种通过甲醇氧化脱氢制备甲醛的方法，该方法包括将含如下组分
a)0.1至50体积％甲醇，
b)0.1至30体积％氧气，
c)0至50体积％氧化氮，和
d)0至60体积％水
的气体混合物(i)在150至800℃下通过磷掺杂银催化剂固定床(a)，并对于每1cm2磷掺杂银催化剂固定床(a)横截面积以气体混合物(i)形式通过的每1kg甲醇，将按磷掺杂银催化剂固定床计，0.01至100ppm(重量)的磷，施于磷掺杂银催化剂固定床(a)上，所述磷为熔点或分解温度高于500℃的细分磷化合物形式。
2.如权利要求1的方法，其中使用的磷掺杂银催化剂固定床(a)可通过如下方法获得：
I.安排通过由银盐水溶液电解淀积银获得的银晶体形成起始银催化剂固定床(a)，和
II.在气体混合物(i)于150至800℃下通过固定床之前，使起始银催化剂固定床(a)与按银计1至20,000ppm(重量)的所述磷化合物形式的磷接触。
3.如权利要求1或2的方法，其中使用的磷掺杂银催化剂固定床(a)由一层或多层最大平均直径0.2至10mm的银晶体构成，总床厚度为1至10cm。
4.如权利要求1至3任何一项的方法，其中使用的所述磷化合物为碱金属或碱土金属的磷酸盐或焦磷酸盐。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19605213.0 | 1996-02-13 | ||
| DE19605213A DE19605213A1 (de) | 1996-02-13 | 1996-02-13 | Verfahren zur Herstellung von Formaldehyd |
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| Publication Number | Publication Date |
|---|---|
| CN1211233A CN1211233A (zh) | 1999-03-17 |
| CN1106373C true CN1106373C (zh) | 2003-04-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97192225A Expired - Fee Related CN1106373C (zh) | 1996-02-13 | 1997-02-11 | 制备甲醛的方法 |
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| Country | Link |
|---|---|
| US (1) | US5990358A (zh) |
| EP (1) | EP0883593B1 (zh) |
| JP (1) | JP2000504703A (zh) |
| KR (1) | KR100501852B1 (zh) |
| CN (1) | CN1106373C (zh) |
| DE (2) | DE19605213A1 (zh) |
| ES (1) | ES2146976T3 (zh) |
| WO (1) | WO1997030015A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6563006B2 (en) | 2001-04-30 | 2003-05-13 | Melvin K. Carter | Catalytic oxidative conversion of hydrocarbons to aldehydes |
| US20080078802A1 (en) | 2006-09-29 | 2008-04-03 | Hess Christopher J | Surgical staples and stapling instruments |
| CN102503786A (zh) * | 2011-11-02 | 2012-06-20 | 天津渤海化工有限责任公司天津碱厂 | 一种聚甲醛生产过程中更换甲醛反应器中的催化剂的方法 |
| JP5861872B2 (ja) * | 2012-01-10 | 2016-02-16 | 三菱マテリアル株式会社 | 銀粘土用銀粉末、銀粘土用銀粉末製造法及びこの銀粉末を含む銀粘土 |
| CN102757324B (zh) * | 2012-05-22 | 2014-07-16 | 山西阳煤丰喜肥业(集团)有限责任公司 | 一种甲醇富氧生产甲醛及甲醛尾气利用方法 |
| US9828322B2 (en) | 2016-01-28 | 2017-11-28 | Eastman Chemical Company | Efficient synthesis of methacroelin and other alpha, beta-unsaturated aldehydes over a regenerable anatase titania catalyst |
| US9834501B2 (en) | 2016-01-28 | 2017-12-05 | Eastman Chemical Company | Efficient synthesis of methacroelin and other alpha, beta—unsaturated aldehydes from methanol and an aldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439625A (en) * | 1982-09-29 | 1984-03-27 | E. I. Du Pont De Nemours And Company | Production of formaldehyde |
| EP0467169A1 (de) * | 1990-07-16 | 1992-01-22 | BASF Aktiengesellschaft | Verfahren zur Herstellung von Formaldehyd |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2462413A (en) * | 1946-06-06 | 1949-02-22 | Allied Chem & Dye Corp | Production of formaldehyde |
| US2587468A (en) * | 1948-03-27 | 1952-02-26 | Monsanto Chemicals | Ethylene oxide process |
| US3948997A (en) * | 1968-05-06 | 1976-04-06 | Laporte Industries Limited | Vapour phase oxidation process |
| BE758502A (fr) * | 1969-11-06 | 1971-05-05 | Basf Ag | Preparation d'alcools et d'aldehydes |
| DE2116947C3 (de) * | 1971-04-07 | 1974-12-19 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Formaldehyd |
| DE2548908C3 (de) * | 1975-10-31 | 1978-04-27 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Formaldehyd |
| US4198351A (en) * | 1977-04-15 | 1980-04-15 | Celanese Corporation | Formaldehyde production process |
| US4167527A (en) * | 1978-01-23 | 1979-09-11 | E. I. Du Pont De Nemours And Company | Methanol oxidation/dehydrogenation over silver-gold alloy |
| US4219509A (en) * | 1978-01-23 | 1980-08-26 | E. I. Du Pont De Nemours And Company | Methanol oxidation/dehydrogenation over silver-gold alloy |
| US4383123A (en) * | 1981-10-08 | 1983-05-10 | Monsanto Company | Manufacture of aqueous formaldehyde |
| CN85100530A (zh) * | 1985-04-01 | 1986-03-10 | 复旦大学 | 银-磷催化剂的制备及在催化氧化醇制醛中的应用 |
| JPH04288034A (ja) * | 1991-03-14 | 1992-10-13 | Mitsui Toatsu Chem Inc | ホルムアルデヒドの製造方法 |
| ATE193226T1 (de) * | 1995-03-15 | 2000-06-15 | Basf Ag | Verfahren zur herstellung von phosphordotierten silberkatalysatoren |
-
1996
- 1996-02-13 DE DE19605213A patent/DE19605213A1/de not_active Withdrawn
-
1997
- 1997-02-11 EP EP97902358A patent/EP0883593B1/de not_active Expired - Lifetime
- 1997-02-11 WO PCT/EP1997/000615 patent/WO1997030015A1/de active IP Right Grant
- 1997-02-11 DE DE59701711T patent/DE59701711D1/de not_active Expired - Lifetime
- 1997-02-11 KR KR10-1998-0706236A patent/KR100501852B1/ko not_active IP Right Cessation
- 1997-02-11 US US09/029,853 patent/US5990358A/en not_active Expired - Fee Related
- 1997-02-11 JP JP9528968A patent/JP2000504703A/ja active Pending
- 1997-02-11 CN CN97192225A patent/CN1106373C/zh not_active Expired - Fee Related
- 1997-02-11 ES ES97902358T patent/ES2146976T3/es not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439625A (en) * | 1982-09-29 | 1984-03-27 | E. I. Du Pont De Nemours And Company | Production of formaldehyde |
| EP0467169A1 (de) * | 1990-07-16 | 1992-01-22 | BASF Aktiengesellschaft | Verfahren zur Herstellung von Formaldehyd |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000504703A (ja) | 2000-04-18 |
| KR19990082503A (ko) | 1999-11-25 |
| DE19605213A1 (de) | 1997-08-14 |
| ES2146976T3 (es) | 2000-08-16 |
| EP0883593A1 (de) | 1998-12-16 |
| DE59701711D1 (de) | 2000-06-21 |
| WO1997030015A1 (de) | 1997-08-21 |
| KR100501852B1 (ko) | 2005-09-27 |
| US5990358A (en) | 1999-11-23 |
| EP0883593B1 (de) | 2000-05-17 |
| CN1211233A (zh) | 1999-03-17 |
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