CN102755897B - Method for preparing catalyst for methanol dehydrogenation to methyl formate through step coprecipitation-spray process - Google Patents
Method for preparing catalyst for methanol dehydrogenation to methyl formate through step coprecipitation-spray process Download PDFInfo
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- CN102755897B CN102755897B CN201210252123.5A CN201210252123A CN102755897B CN 102755897 B CN102755897 B CN 102755897B CN 201210252123 A CN201210252123 A CN 201210252123A CN 102755897 B CN102755897 B CN 102755897B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 35
- 239000007921 spray Substances 0.000 title description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000000084 colloidal system Substances 0.000 claims abstract description 43
- 239000012065 filter cake Substances 0.000 claims abstract description 41
- 239000010949 copper Substances 0.000 claims abstract description 28
- 238000000975 co-precipitation Methods 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 15
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 117
- 230000032683 aging Effects 0.000 claims description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- 238000001354 calcination Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 28
- 238000003801 milling Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- 229920002472 Starch Polymers 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 22
- 235000019698 starch Nutrition 0.000 claims description 22
- 238000009938 salting Methods 0.000 claims description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000008107 starch Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000012066 reaction slurry Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000012266 salt solution Substances 0.000 abstract description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 47
- 238000003756 stirring Methods 0.000 description 45
- 238000012360 testing method Methods 0.000 description 32
- 239000013589 supplement Substances 0.000 description 30
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 30
- 239000002994 raw material Substances 0.000 description 28
- 239000003513 alkali Substances 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 16
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 238000013467 fragmentation Methods 0.000 description 9
- 238000006062 fragmentation reaction Methods 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000000748 compression moulding Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003835 carbonate co-precipitation Methods 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing catalyst for methanol dehydrogenation to methyl formate through a step coprecipitation-spray drying process. The method is that step coprecipitation is performed to copper, zinc and aluminum salt solution and alkaline solution, after the copper, zinc and aluminum salt solution and alkaline solution are pulped and filtered with hot desalted water, a qualified filter cake is obtained and is subjected to colloid mill processing, spray drying is performed to size, and dried catalyst precursor is roasted and formed so as to obtain the catalyst for methanol dehydrogenation. The catalyst prepared by the method has the characteristics of high catalytic activity and selectivity and strong stability.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, particularly the method for copper base methanol dehydrogenation methyl formate catalyst processed in chemical field, belongs to catalyst preparation technical field.
Background technology
In Coal Chemical Industry and field of fine chemical, copper-based catalysts is widely applied in many hydrogenation, dehydrogenation and reformation hydrogen production gas-solid phase reaction, prepares the reactions such as methyl alcohol, hydrogen production from methanol-steam reforming, carbon monoxide under low temperature conversion such as methanol dehydrogenation methyl formate processed, mesolow synthesis gas.The key component of copper-based catalysts is generally CuO, ZnO and Al
2o
3, the traditional copper-based catalysts product mainly nitrate by Cu, Zn, tri-kinds of metal components of Al and alkali carries out that coprecipitation reaction is synthetic to be obtained.For example, patent CN200410053253.1 discloses copper-based catalysts of a kind of nano-carbon material modification and preparation method thereof, described catalyst adopts carbonate co-precipitation legal system standby, be about to the reactor that the nitrate of Cu, Zn, Al and sodium carbonate liquor constant speed drip enter to preset metering nano-carbon material and carry out coprecipitation reaction, through steps such as washing, dry, roastings, make.
There is larger limitation in traditional copper-based catalysts preparation technology, the Study on Microstructure of catalyst is found, the copper-based catalysts crystal formation of preparing by traditional coprecipitation method is random state, the particle diameter of CuO crystallite distributes, pore-size distribution is all very inhomogeneous, the specific area of catalyst is less, thereby the catalytic activity that has caused copper-based catalysts, particularly selective and heat endurance is relatively low, the service life of catalyst is relatively short.
Formamide has active reactivity and special solvability, can be used as organic synthesis raw material, paper treating agent, and the softening agent of fiber industry, the softening agent of animal glue, also as the analytical reagent of measuring amino acid content in rice.In organic synthesis, the purposes of medical aspect is in the majority, is also having a lot of purposes aspect agricultural chemicals, dyestuff, pigment, spices, auxiliary agent.Also be good organic solvent, be mainly used in the spinning and ion exchange resin of acrylonitrile copolymer, and the covering with paint of the antistatic of plastic products or conduction covering with paint etc.At present, the benzamide type product such as domestic formamide, dimethyl formamide generally adopts the methanol dehydrogenation methyl formate processed of Southwest Chemical Research and Design Institute independent development and the processing technology routine of the synthetic formamide of methyl formate amination two steps reaction.Methanol dehydrogenation methyl formate technique processed has the following advantages with respect to Methyl Formate from Carbonylation of Methanol tool: (1) technology investment scale is less; (2) reaction condition is relatively gentle, can under the condition of 180～280 ℃ of reaction temperatures ,～0.1MPa, react; (3) raw material is relatively single and be easy to get; (4) device can by-product purity the hydrogen that is 85%, after separating-purifying, can be used for other relevant hydrogenation plants.But, current methanol dehydrogenation methyl formate catalyst processed generally adopts copper-based catalysts, due to copper-based catalysts preparation technology feature, it is relatively low that the methyl alcohol conversion per pass of catalyst and methyl formate are selective etc., the conversion per pass of general methyl alcohol is lower than 30%, methyl formate selectively lower than 85%, generate the gaseous impurities such as carbon monoxide, carbon dioxide and methane of high level.And a large amount of unreacted methyl alcohol circulates in system, has increased to a certain extent the production cost of energy resource consumption and methyl formate.
In sum, must develop the preparation technology of the copper base methanol dehydrogenation methyl formate catalyst processed making new advances, the particle diameter that improves CuO crystallite in catalyst distributes and pore-size distribution, thereby improves the catalytic performances such as the selective and stability of methanol conversion, the methyl formate of catalyst.
In the technology of numerous solid catalyst moulding, spray drying forming be prepared sizes evenly and be the important means of spherical finely grained catalyst, and in the preparation of all multi-catalysts, obtained good application.The dry powder product that is often used to produce natural plant extracts, medical product, food and biochemical product of spraying.The features such as spraying pyrolysis technique is the emerging method of preparing powder body material, and powder body material particle diameter prepared by this technology is evenly distributed, specific area is large and the mobility of particle is better.In addition, the advantage that powder body material also has other is prepared in spraying thermal decomposition: (1) raw material mixes under solution state, can guarantee uniform component distribution, and technical process is simple, component loss is few, can accurately control stoichiometric proportion, is especially applicable to preparing multicomponent composite powder; (2) micro mist is by being suspended in airborne droplet drying, and particle is generally the spherical of rule, and few reunion, without follow-up washing, grinds, and has guaranteed the high-purity of product, high activity; (3) whole process completed rapidly in short several seconds, so drop has little time to occur solute segregation in course of reaction, further guaranteed the homogeneity that component distributes; (4) operation is simple, and a step obtains finished product, and without filtration, washing, dry, crushing process, simple to operation, production process is continuous, and production capacity is large, and production efficiency is high, is very beneficial for large suitability for industrialized production.
In addition, the appearance of colloid mill just becomes the another kind of important channel of preparation nano material.Along with deepening continuously of research, also become a kind of very important method in catalysis material research field.The main purpose of colloid mill effect is to reduce particle size, changes grain shape, the particle of heterogeneity is uniformly dispersed, and generally can relate to the variation of structure.
Summary of the invention
The object of the present invention is to provide a kind of dry method of preparing copper base methanol dehydrogenation methyl formate catalyst processed of multiple step coprecipitation-spraying, by traditional co-precipitation preparation method and colloid mill technology, spray drying technology, combine, improve the microstructure of catalyst, improve the catalytic activity of methanol dehydrogenation methyl formate catalyst processed, selective and stability, thereby further improve methanol dehydrogenation methyl formate technology level processed.
In order to realize foregoing invention object, the present invention adopts following technical proposals:
A kind of dry method of preparing copper base methanol dehydrogenation methyl formate catalyst processed of multiple step coprecipitation-spraying, comprise first copper, zinc, aluminum salt solution and alkaline solution are carried out to multiple step coprecipitation, then after filtering with hot desalted water making beating, qualified cake carries out milling treatment of colloid, then slurry is sprayed dry, dried catalyst precursor is calcined, moulding makes Catalysts of Methanol Dehydrogenation.
Particularly, said method comprises the steps:
1) adopt salting liquid containing zinc, aluminium under certain precipitation temperature and pH value condition, to carry out co-precipitation with alkaline solution and react, and carry out aging generation catalyst carrier;
2) adopt salting liquid and the alkaline solution preheating at a certain temperature of cupric, zinc, aluminium, then join in the catalyst carrier of producing in step (1), carry out co-precipitation reaction at a certain temperature with under pH value condition, and carry out aging generation catalyst reaction slurry;
3) by after the reaction paste centrifugal filtration generating in step (2), add desalted water to starch again, again filter, repeatedly starch filter process again until catalyst filter cake impurity content is qualified;
4), in the qualified cake obtaining in step (3), add desalted water to carry out milling treatment of colloid;
5) slurry after milling treatment of colloid in step (4) is sprayed and is dried;
6) the dried catalyst precursor of spraying in step (5) is carried out to high-temperature calcination and moulding.
In the method for the invention, the salt of copper, zinc, aluminium is preferably nitrate; Alkaline solution is preferably the aqueous solution of NaOH, potassium hydroxide or sodium carbonate, is especially preferably aqueous sodium carbonate.
In above-mentioned preparation method, step 1 relates to the precipitation reaction of catalyst carrier, and wherein preferably precipitation temperature is 60-90 ℃, more preferably 65-80 ℃; The pH value of precipitation reaction is preferably 6.5-9.0, more preferably 7.0-8.5; The preferred 0.5-2 hour of ageing time, more preferably 0.75-1.5h.
In above-mentioned preparation method, step 2 relates to the precipitation reaction of catalyst main active component, and wherein preferably temperature is 65-90 ℃, more preferably 70-80 ℃; Precipitation reaction pH value is preferably 6.5-9.0, more preferably 7.0-8.5; The preferred 0.5-2 hour of ageing time, more preferably 0.75-1.5h.
In above-mentioned preparation method, the amount that in the process of slurry again of step 3 reaction paste, desalted water adds is 1-10 times of filter cake volume, and temperature is 60-90 ℃, and preferably the temperature of desalted water is 65-75 ℃; Slurry filters preferred 3-5 time again, more preferably 3 times; Wherein impurity content is qualified refers to that in filter cake, Na ion concentration is down to below 0.01-0.001%, is preferably down to below 0.001%.
In above-mentioned preparation method, the gap of the colloid mill of step 4 is 0.1-5mm, preferred 0.1-1.0mm, and the amount that desalted water adds is 1-10 times of filter cake volume.
In above-mentioned preparation method, in the spray-drying process of step 5, EAT is 180-280 ℃, preferably 210-250 ℃; Charging rate is 300-3000ml/h, is preferably 1000-1500ml/h; In spray-drying process, the ratio of catalyst feed and water is 1:1-1:10, and preferred proportion is 1:3-1:6.
In above-mentioned preparation method, after the spraying of step 6 is dry, powder calcining heat is: 280-400 ℃, preferably 290-350 ℃; Material calcination time is: 2-10h, preferably 3-6h.
In above-mentioned preparation method, the composition of catalyst (atomic ratio) is Cu:Zn:Al=(4～8): (1～5): (0.5～3), the composition of preferred catalyst (atomic ratio) is Cu:Zn:Al=(5～7): (2～4): (1～2).
Compare with existing copper base methanol dehydrogenation methyl formate catalyst preparation technology processed, the present invention has advantage as described below:
(1) adopt advanced multiple step coprecipitation technique, first form the catalyst carrier with peptizaiton, catalyst activity component CuO crystallite is more disperseed, the particle diameter of crystal is less, thereby improves the catalytic performance of catalyst;
(2) adopt advanced milling treatment of colloid technology, catalyst precursor filter cake is carried out to effective fragmentation, form granule slurry very even, that disperse, be conducive to improve the spraying drying effect of catalyst precursor, thereby finally improve the catalytic performance of catalyst;
(3) adopt advanced spray drying technology, the particle diameter of catalyst precursor is more evenly distributed, specific area is larger and particle is more complete and mobility is better, is conducive to improve the catalytic activity of catalyst, selective and stability;
(4) the copper base methanol dehydrogenation methyl formate catalyst processed that adopts the technology of the present invention to prepare, the activity of catalyst improves 10-30%, and the methyl formate of catalyst selectively improves 5-15%.
The specific embodiment
Below in conjunction with the specific embodiment, the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realizing based on content of the present invention all belong to scope of the present invention.
implement 1
Take zinc nitrate 5.20g, aluminum nitrate 13.12g, be dissolved in and be equipped with in 50ml desalted water beaker, stir it is dissolved completely, supplement desalted water and be settled to 85ml, preparation obtains a step salting liquid.Weighing sodium carbonate 7.71g, is dissolved in and is equipped with in 50ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 85ml, and preparation obtains a step aqueous slkali.Take copper nitrate 197.22g, zinc nitrate 64.18g, aluminum nitrate 30.62g, be dissolved in and be equipped with in 200ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and be settled to 1000ml, and preparation obtains two step salting liquids.Weighing sodium carbonate 127.19g, is dissolved in and is equipped with in 200ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 1000ml, and preparation obtains two step aqueous slkalis.
One step salt and a step alkali are carried out to preheating, be preheated to 65 ℃ of reaction temperatures, control reaction water bath temperature is 65 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and carries out coprecipitation reaction in reactor, while vigorous stirring, reaction paste pH value is 6.7, has reacted latter aging 1 hour.
In one step precipitation slurry ageing process, two step salt and two step alkali are carried out to preheating, be preheated to 70 ℃ of reaction temperatures, control reaction water bath temperature is 70 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and in reactor, carries out coprecipitation reaction, simultaneously vigorous stirring, reaction paste pH value is 6.8, has reacted latter aging 1 hour.
Reaction paste after aging completing adopts filter centrifugal to filter out most mother liquor, and filter cake adopts 3000ml desalted water to starch again, more again carries out centrifugal filtration after having starched.Repeating 2-3 time starches and filters until the Na ion concentration in filter cake is down to below 0.01% again.
Slurry filters after qualified and obtains 500ml filter cake again, carries out milling treatment of colloid, and colloid mill gap adjustment is 0.5mm, adds 1500ml, the desalted water of 65 ℃ in filter cake, slowly adds and in colloid mill hopper, carries out milling treatment of colloid.
Slurry after milling treatment of colloid, delivers to spray dryer and sprays dry.EAT is adjusted to 220 ℃, and charging rate is adjusted to 1000ml/h.
Spraying has been dried the dry powder 130g of rear taking-up catalyst precursor, puts into calcining furnace and calcines, and calcining heat is 350 ℃, and calcination time is 5 hours.
After calcining, obtain catalyst powder 93.5g, add appropriate graphite and water fully to mix after cooling, then carry out compression molding and obtain the methanol dehydrogenation methyl formate catalyst A processed 100g that atomic ratio is 7:2:1.
The active testing of catalyst the results are shown in following table.
table 1 Catalysts of Methanol Dehydrogenation active testing result
| Catalyst | Methanol conversion (%) | Heat-resisting rear methanol conversion (%) | Methyl formate selective (%) | Heat-resisting rear methyl formate selective (%) |
| Catalyst A | 37.0 | 35.0 | 93.5 | 90.0 |
Activity rating condition:
Catalyst granules: Φ 5 * 5mm after moulding is 20-40 order after fragmentation;
Catalytic amount: 4ml;
Reaction condition: 210 ℃, normal pressure, liquid air speed 1.0h
-1;
Raw material forms (volume ratio): 99.50%CH
3oH,, 0.50% H
2o.
Overheat test condition: overheated 10h under 350 ℃ of conditions, 210 ℃, normal pressure, liquid air speed 1.0h
-1active testing under condition.
embodiment 2
take zinc nitrate 9.71g, aluminum nitrate 24.50g, be dissolved in and be equipped with in 80ml desalted water beaker, stir it is dissolved completely, supplement desalted water and be settled to 160ml, preparation obtains a step salting liquid.Weighing sodium carbonate 15.07g, is dissolved in and is equipped with in 80ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 160ml, and preparation obtains a step aqueous slkali.Take copper nitrate 197.22g, zinc nitrate 184.57g, aluminum nitrate 34.75g, be dissolved in and be equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and be settled to 1000ml, and preparation obtains two step salting liquids.Weighing sodium carbonate 182.77g, is dissolved in and is equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 1500ml, and preparation obtains two step aqueous slkalis.
One step salt and a step alkali are carried out to preheating, be preheated to 70 ℃ of reaction temperatures, control reaction water bath temperature is 70 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and carries out coprecipitation reaction in reactor, while vigorous stirring, reaction paste pH value is 7.6, has reacted latter aging 0.75 hour.
In one step precipitation slurry ageing process, two step salt and two step alkali are carried out to preheating, be preheated to 85 ℃ of reaction temperatures, control reaction water bath temperature is 85 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and in reactor, carries out coprecipitation reaction, simultaneously vigorous stirring, reaction paste pH value is 7.5, has reacted latter aging 1 hour.
Reaction paste after aging completing adopts filter centrifugal to filter out most mother liquor, and filter cake adopts 3000ml desalted water to starch again, more again carries out centrifugal filtration after having starched.Repeating 2-3 time starches and filters until the Na ion concentration in filter cake is down to below 0.01% again.
Slurry filters after qualified and obtains 750ml filter cake again, carries out milling treatment of colloid, and colloid mill gap adjustment is 0.2mm, adds 2500ml, the desalted water of 70 ℃ in filter cake, slowly adds and in colloid mill hopper, carries out milling treatment of colloid.
Slurry after milling treatment of colloid, delivers to spray dryer and sprays dry.EAT is adjusted to 200 ℃, and charging rate is adjusted to 1200ml/h.
Spraying has been dried the dry powder 195g of rear taking-up catalyst precursor, puts into calcining furnace and calcines, and calcining heat is 320 ℃, and calcination time is 6 hours.
After calcining, obtain catalyst powder 133.0g, add appropriate graphite and water fully to mix after cooling, then carry out compression molding and obtain the methanol dehydrogenation methyl formate catalyst B processed 145.0g that atomic ratio is 5:4:1.
The active testing of catalyst the results are shown in following table.
table 2 Catalysts of Methanol Dehydrogenation active testing result
| Catalyst | Methanol conversion (%) | Heat-resisting rear methanol conversion (%) | Methyl formate selective (%) | Heat-resisting rear methyl formate selective (%) |
| Catalyst B | 39.0 | 35.0 | 95.0 | 93.0 |
Activity rating condition:
Catalyst granules: Φ 5 * 5mm after moulding is 20-40 order after fragmentation;
Catalytic amount: 4ml;
Reaction condition: 210 ℃, normal pressure, liquid air speed 1.0h
-1;
Raw material forms (volume ratio): 99.50%CH
3oH,, 0.50% H
2o.
Overheat test condition: overheated 10h under 350 ℃ of conditions, 210 ℃, normal pressure, liquid air speed 1.0h
-1active testing under condition.
embodiment 3
take zinc nitrate 16.19g, aluminum nitrate 40.83g, be dissolved in and be equipped with in 100ml desalted water beaker, stir it is dissolved completely, supplement desalted water and be settled to 250ml, preparation obtains a step salting liquid.Weighing sodium carbonate 26.27g, is dissolved in and is equipped with in 100ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 250ml, and preparation obtains a step aqueous slkali.Take copper nitrate 197.22g, zinc nitrate 105.24g, aluminum nitrate 10.21g, be dissolved in and be equipped with in 300ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and be settled to 1200ml, and preparation obtains two step salting liquids.Weighing sodium carbonate 146.1g, is dissolved in and is equipped with in 300ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 1200ml, and preparation obtains two step aqueous slkalis.
One step salt and a step alkali are carried out to preheating, be preheated to 70 ℃ of reaction temperatures, control reaction water bath temperature is 70 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and carries out coprecipitation reaction in reactor, while vigorous stirring, reaction paste pH value is 7.8, has reacted rear aging 0.5h.
In one step precipitation slurry ageing process, two step salt and two step alkali are carried out to preheating, be preheated to 75 ℃ of reaction temperatures, control reaction water bath temperature is 75 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and in reactor, carries out coprecipitation reaction, simultaneously vigorous stirring, reaction paste pH value is 8.0, has reacted rear aging 0.45h.
Reaction paste after aging completing adopts filter centrifugal to filter out most mother liquor, and filter cake adopts 3000ml desalted water to starch again, more again carries out centrifugal filtration after having starched.Repeating 2-3 time starches and filters until the Na ion concentration in filter cake is down to below 0.01% again.
Slurry filters after qualified and obtains 550ml filter cake again, carries out milling treatment of colloid, and colloid mill gap adjustment is 0.8mm, adds 2000ml, the desalted water of 72 ℃ in filter cake, slowly adds and in colloid mill hopper, carries out milling treatment of colloid.
Slurry after milling treatment of colloid, delivers to spray dryer and sprays dry.EAT is adjusted to 225 ℃, and charging rate is adjusted to 1500ml/h.
Spraying has been dried the dry powder 150g of rear taking-up catalyst precursor, puts into calcining furnace and calcines, and calcining heat is 340 ℃, and calcination time is 5.5 hours.
After calcining, obtain catalyst powder 103.5g, add appropriate graphite and water fully to mix after cooling, then carry out compression molding and obtain the methanol dehydrogenation methyl formate catalyst processed C112.0g that atomic ratio is 6:3:1.
The active testing of catalyst the results are shown in following table.
table 3 Catalysts of Methanol Dehydrogenation active testing result
| Catalyst | Methanol conversion (%) | Heat-resisting rear methanol conversion (%) | Methyl formate selective (%) | Heat-resisting rear methyl formate selective (%) |
| Catalyst C | 38.0 | 36.0 | 97.0 | 95.0 |
Activity rating condition:
Catalyst granules: Φ 5 * 5mm after moulding is 20-40 order after fragmentation;
Catalytic amount: 4ml;
Reaction condition: 210 ℃, normal pressure, liquid air speed 1.0h
-1;
Raw material forms (volume ratio): 99.50%CH
3oH,, 0.50% H
2o.
Overheat test condition: overheated 10h under 350 ℃ of conditions, 210 ℃, normal pressure, liquid air speed 1.0h
-1active testing under condition.
embodiment 4
take zinc nitrate 23.18g, aluminum nitrate 58.46g, be dissolved in and be equipped with in 100ml desalted water beaker, stir it is dissolved completely, supplement desalted water and be settled to 400ml, preparation obtains a step salting liquid.Weighing sodium carbonate 35.97g, is dissolved in and is equipped with in 100ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 400ml, and preparation obtains a step aqueous slkali.Take copper nitrate 197.22g, zinc nitrate 109.28g, aluminum nitrate 25.05g, be dissolved in and be equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and be settled to 1200ml, and preparation obtains two step salting liquids.Weighing sodium carbonate 134.70g, is dissolved in and is equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 1200ml, and preparation obtains two step aqueous slkalis.
One step salt and a step alkali are carried out to preheating, be preheated to 70 ℃ of reaction temperatures, control reaction water bath temperature is 70 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and carries out coprecipitation reaction in reactor, while vigorous stirring, reaction paste pH value is 7.2, has reacted rear aging 1h.
In one step precipitation slurry ageing process, two step salt and two step alkali are carried out to preheating, be preheated to 75 ℃ of reaction temperatures, control reaction water bath temperature is 75 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and in reactor, carries out coprecipitation reaction, simultaneously vigorous stirring, reaction paste pH value is 7.4, has reacted rear aging 0.45h.
Reaction paste after aging completing adopts filter centrifugal to filter out most mother liquor, and filter cake adopts 3000ml desalted water to starch again, more again carries out centrifugal filtration after having starched.Repeating 2-3 time starches and filters until the Na ion concentration in filter cake is down to below 0.01% again.
Slurry filters after qualified and obtains 700ml filter cake again, carries out milling treatment of colloid, and colloid mill gap adjustment is 0.6mm, adds 3000ml, the desalted water of 70 ℃ in filter cake, slowly adds and in colloid mill hopper, carries out milling treatment of colloid.
Slurry after milling treatment of colloid, delivers to spray dryer and sprays dry.EAT is adjusted to 210 ℃, and charging rate is adjusted to 1200ml/h.
Spraying has been dried the dry powder 160g of rear taking-up catalyst precursor, puts into calcining furnace and calcines, and calcining heat is 340 ℃, and calcination time is 6 hours.
After calcining, obtain catalyst powder 110.0g, add appropriate graphite and water fully to mix after cooling, then carry out compression molding and obtain the methanol dehydrogenation methyl formate catalyst processed D120.0g that atomic ratio is 5.5:3.0:1.5.
The active testing of catalyst the results are shown in following table.
table 4 Catalysts of Methanol Dehydrogenation active testing result
| Catalyst | Methanol conversion (%) | Heat-resisting rear methanol conversion (%) | Methyl formate selective (%) | Heat-resisting rear methyl formate selective (%) |
| Catalyst D | 35.0 | 33.0 | 94.5 | 91.8 |
Activity rating condition:
Catalyst granules: Φ 5 * 5mm after moulding is 20-40 order after fragmentation;
Catalytic amount: 4ml;
Reaction condition: 210 ℃, normal pressure, liquid air speed 1.0h
-1;
Raw material forms (volume ratio): 99.50%CH
3oH,, 0.50% H
2o.
Overheat test condition: overheated 10h under 350 ℃ of conditions, 210 ℃, normal pressure, liquid air speed 1.0h
-1active testing under condition.
embodiment 5
take zinc nitrate 20.24g, aluminum nitrate 51.04g, be dissolved in and be equipped with in 100ml desalted water beaker, stir it is dissolved completely, supplement desalted water and be settled to 350ml, preparation obtains a step salting liquid.Weighing sodium carbonate 31.40g, is dissolved in and is equipped with in 100ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 350ml, and preparation obtains a step aqueous slkali.Take copper nitrate 197.22g, zinc nitrate 60.71g, aluminum nitrate 51.04g, be dissolved in and be equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and be settled to 1200ml, and preparation obtains two step salting liquids.Weighing sodium carbonate 128.47g, is dissolved in and is equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 1200ml, and preparation obtains two step aqueous slkalis.
One step salt and a step alkali are carried out to preheating, be preheated to 65 ℃ of reaction temperatures, control reaction water bath temperature is 65 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and carries out coprecipitation reaction in reactor, while vigorous stirring, reaction paste pH value is 6.7, has reacted rear aging 1h.
In one step precipitation slurry ageing process, two step salt and two step alkali are carried out to preheating, be preheated to 80 ℃ of reaction temperatures, control reaction water bath temperature is 80 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and in reactor, carries out coprecipitation reaction, simultaneously vigorous stirring, reaction paste pH value is 6.8, has reacted rear aging 0.45h.
Reaction paste after aging completing adopts filter centrifugal to filter out most mother liquor, and filter cake adopts 3000ml desalted water to starch again, more again carries out centrifugal filtration after having starched.Repeating 2-3 time starches and filters until the Na ion concentration in filter cake is down to below 0.01% again.
Slurry filters after qualified and obtains 500ml filter cake again, carries out milling treatment of colloid, and colloid mill gap adjustment is 0.5mm, adds 1500ml, the desalted water of 68 ℃ in filter cake, slowly adds and in colloid mill hopper, carries out milling treatment of colloid.
Slurry after milling treatment of colloid, delivers to spray dryer and sprays dry.EAT is adjusted to 220 ℃, and charging rate is adjusted to 1000ml/h.
Spraying has been dried the dry powder 145g of rear taking-up catalyst precursor, puts into calcining furnace and calcines, and calcining heat is 295 ℃, and calcination time is 6 hours.
After calcining, obtain catalyst powder 99.0g, add appropriate graphite and water fully to mix after cooling, then carry out compression molding and obtain the methanol dehydrogenation methyl formate catalyst processed E107.6g that atomic ratio is 6:2:2.
The active testing of catalyst the results are shown in following table.
table 5 Catalysts of Methanol Dehydrogenation active testing result
| Catalyst | Methanol conversion (%) | Heat-resisting rear methanol conversion (%) | Methyl formate selective (%) | Heat-resisting rear methyl formate selective (%) |
| Catalyst E | 36 | 34 | 94.0 | 92.0 |
Activity rating condition:
Catalyst granules: Φ 5 * 5mm after moulding is 20-40 order after fragmentation;
Catalytic amount: 4ml;
Reaction condition: 210 ℃, normal pressure, liquid air speed 1.0h
-1;
Raw material forms (volume ratio): 99.50%CH
3oH,, 0.50% H
2o.
Overheat test condition: overheated 10h under 350 ℃ of conditions, 210 ℃, normal pressure, liquid air speed 1.0h
-1active testing under condition.
embodiment 6
take zinc nitrate 11.21g, aluminum nitrate 28.27g, be dissolved in and be equipped with in 50ml desalted water beaker, stir it is dissolved completely, supplement desalted water and be settled to 180ml, preparation obtains a step salting liquid.Weighing sodium carbonate 18.97g, is dissolved in and is equipped with in 50ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 180ml, and preparation obtains a step aqueous slkali.Take copper nitrate 197.22g, zinc nitrate 82.20g, aluminum nitrate 18.84g, be dissolved in and be equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and be settled to 1100ml, and preparation obtains two step salting liquids.Weighing sodium carbonate 147.05g, is dissolved in and is equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 1100ml, and preparation obtains two step aqueous slkalis.
One step salt and a step alkali are carried out to preheating, be preheated to 75 ℃ of reaction temperatures, control reaction water bath temperature is 75 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and carries out coprecipitation reaction in reactor, while vigorous stirring, reaction paste pH value is 7.5, has reacted latter aging 1.0 hours.
In one step precipitation slurry ageing process, two step salt and two step alkali are carried out to preheating, be preheated to 75 ℃ of reaction temperatures, control reaction water bath temperature is 75 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and in reactor, carries out coprecipitation reaction, simultaneously vigorous stirring, reaction paste pH value is 8.0, has reacted latter aging 1.5 hours.
Reaction paste after aging completing adopts filter centrifugal to filter out most mother liquor, and filter cake adopts 3000ml desalted water to starch again, more again carries out centrifugal filtration after having starched.Repeating 2-3 time starches and filters until the Na ion concentration in filter cake is down to below 0.01% again.
Slurry filters after qualified and obtains 500ml filter cake again, carries out milling treatment of colloid, and colloid mill gap adjustment is 0.5mm, adds 2500ml, the desalted water of 75 ℃ in filter cake, slowly adds and in colloid mill hopper, carries out milling treatment of colloid.
Slurry after milling treatment of colloid, delivers to spray dryer and sprays dry.EAT is adjusted to 220 ℃, and charging rate is adjusted to 1300ml/h.
Spraying has been dried the dry powder 130g of rear taking-up catalyst precursor, puts into calcining furnace and calcines, and calcining heat is 340 ℃, and calcination time is 4 hours.
After calcining, obtain catalyst powder 94.9g, add appropriate graphite and water fully to mix after cooling, then carry out compression molding and obtain the methanol dehydrogenation methyl formate catalyst processed F103.0g that atomic ratio is 6.5:2.5:1.
The active testing of catalyst the results are shown in following table.
table 6 Catalysts of Methanol Dehydrogenation active testing result
| Catalyst | Methanol conversion (%) | Heat-resisting rear methanol conversion (%) | Methyl formate selective (%) | Heat-resisting rear methyl formate selective (%) |
| Catalyst A | 38.0 | 35.0 | 95.0 | 92.0 |
Activity rating condition:
Catalyst granules: Φ 5 * 5mm is 20-40 order after fragmentation;
Catalytic amount: 4ml;
Reaction condition: 210 ℃, normal pressure, liquid air speed 1.0h
-1;
Raw material forms (volume ratio): 99.50%CH
3oH,, 0.50% H
2o.
Overheat test condition: overheated 10h under 350 ℃ of conditions, 210 ℃, normal pressure, liquid air speed 1.0h
-1active testing under condition.
comparative example 1
take zinc nitrate 5.20g, aluminum nitrate 13.12g, be dissolved in and be equipped with in 50ml desalted water beaker, stir it is dissolved completely, supplement desalted water and be settled to 85ml, preparation obtains a step salting liquid.Weighing sodium carbonate 7.71g, is dissolved in and is equipped with in 50ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 85ml, and preparation obtains a step aqueous slkali.Take copper nitrate 197.22g, zinc nitrate 64.18g, aluminum nitrate 30.62g, be dissolved in and be equipped with in 200ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and be settled to 1000ml, and preparation obtains two step salting liquids.Weighing sodium carbonate 127.19g, is dissolved in and is equipped with in 200ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 1000ml, and preparation obtains two step aqueous slkalis.
One step salt and a step alkali are carried out to preheating, be preheated to 65 ℃ of reaction temperatures, control reaction water bath temperature is 65 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and carries out coprecipitation reaction in reactor, while vigorous stirring, reaction paste pH value is 6.7, has reacted rear aging 1h.
In one step precipitation slurry ageing process, two step salt and two step alkali are carried out to preheating, be preheated to 70 ℃ of reaction temperatures, control reaction water bath temperature is 70 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and in reactor, carries out coprecipitation reaction, simultaneously vigorous stirring, reaction paste pH value is 6.8, has reacted rear aging 1h.
Reaction paste after aging completing adopts filter centrifugal to filter out most mother liquor, and filter cake adopts 3000ml desalted water to starch again, more again carries out centrifugal filtration after having starched.Repeating 2-3 time starches and filters until the Na ion concentration in filter cake is down to below 0.01% again.
Slurry filters after qualified and obtains 500ml filter cake again, puts into baking oven and is dried, and baking temperature is 120 ℃, and be 15 hours drying time.After dry, obtain catalyst precursor powder 132g, then put into calcining furnace and calcine, calcining heat is 350 ℃, and calcination time is 5 hours.
After calcining, obtain catalyst powder 94.8g, add appropriate graphite and water fully to mix after cooling, then carry out compression molding and obtain the methanol dehydrogenation methyl formate catalyst A processed that atomic ratio is 7:2:1
1103g.
The active testing of catalyst the results are shown in following table.
table 7 Catalysts of Methanol Dehydrogenation active testing result
| Catalyst | Methanol conversion (%) | Heat-resisting rear methanol conversion (%) | Methyl formate selective (%) | Heat-resisting rear methyl formate selective (%) |
| Catalyst A 1 | 30 | 25 | 84 | 80 |
Activity rating condition:
Catalyst granules: Φ 5 * 5mm is 20-40 order after fragmentation;
Catalytic amount: 4ml;
Reaction condition: 210 ℃, normal pressure, liquid air speed 1.0h
-1;
Raw material forms (volume ratio): 99.50%CH
3oH,, 0.50% H
2o.
Overheat test condition: overheated 10h under 350 ℃ of conditions, 210 ℃, normal pressure, liquid air speed 1.0h
-1active testing under condition.
comparative example 2
take copper nitrate 197.22g, zinc nitrate 69.39g, aluminum nitrate 43.75g, be dissolved in and be equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and be settled to 1200ml, and preparation obtains salting liquid.Weighing sodium carbonate 134.90g, is dissolved in and is equipped with in 500ml desalted water beaker, stirs it is dissolved completely, supplements desalted water and is settled to 1200ml, and preparation obtains aqueous slkali.
Raw material salt solution and raw material aqueous slkali are carried out to preheating, be preheated to 70 ℃ of reaction temperatures, control reaction water bath temperature is 70 ℃ simultaneously, when raw material is saline and alkaline and bath temperature reaches after requirement, and stream adds and carries out coprecipitation reaction in reactor, while vigorous stirring, reaction paste pH value is 6.8, has reacted rear aging 1h.
Reaction paste after aging completing adopts filter centrifugal to filter out most mother liquor, and filter cake adopts 3000ml desalted water to starch again, more again carries out centrifugal filtration after having starched.Repeating 2-3 time starches and filters until the Na ion concentration in filter cake is down to below 0.01% again.
Slurry filters after qualified and obtains 400ml filter cake again, puts into baking oven and is dried, and baking temperature is 120 ℃, and be 15 hours drying time.After dry, obtain catalyst precursor powder 125g, then put into calcining furnace and calcine, calcining heat is 350 ℃, and calcination time is 5 hours.
After calcining, obtain catalyst powder 93.5g, add appropriate graphite and water fully to mix after cooling, then carry out compression molding and obtain the methanol dehydrogenation methyl formate catalyst A processed that atomic ratio is 7:2:1
2101.0g.
The active testing of catalyst the results are shown in following table.
table 8 Catalysts of Methanol Dehydrogenation active testing result
| Catalyst | Methanol conversion (%) | Heat-resisting rear methanol conversion (%) | Methyl formate selective (%) | Heat-resisting rear methyl formate selective (%) |
| Catalyst A 2 | 28.0 | 24.0 | 82.0 | 78.0 |
Activity rating condition:
Catalyst granules: Φ 5 * 5mm is 20-40 order after fragmentation;
Catalytic amount: 4ml;
Reaction condition: 210 ℃, normal pressure, liquid air speed 1.0h
-1;
Raw material forms (volume ratio): 99.50%CH
3oH,, 0.50% H
2o.
Overheat test condition: overheated 10h under 350 ℃ of conditions, 210 ℃, normal pressure, liquid air speed 1.0h
-1active testing under condition.
Claims (15)
1. the dry method of preparing copper base methanol dehydrogenation methyl formate catalyst processed of multiple step coprecipitation-spraying, comprises the steps:
1) adopt salting liquid containing zinc, aluminium under certain precipitation temperature and pH value condition, to carry out co-precipitation with alkaline solution and react, and carry out aging generation catalyst carrier;
2) adopt salting liquid and the alkaline solution preheating at a certain temperature of cupric, zinc, aluminium, then join in the catalyst carrier of producing in step (1), carry out co-precipitation reaction at a certain temperature with under pH value condition, and carry out aging generation catalyst reaction slurry;
3) by after the reaction paste centrifugal filtration generating in step (2), add hot desalted water to starch again, again filter, repeatedly starch filter process again until catalyst filter cake impurity content is qualified;
4), in the qualified cake obtaining in step (3), add hot desalted water to carry out milling treatment of colloid;
5) slurry after milling treatment of colloid in step (4) is sprayed and is dried;
6) the dried catalyst precursor of spraying in step (5) is carried out to high-temperature calcination and moulding; Described calcining heat is 280-400 ℃, and calcination time is 2-10h.
2. the method for claim 1, the salt of wherein said copper, zinc, aluminium is nitrate; Alkaline solution is the aqueous solution of NaOH, potassium hydroxide or sodium carbonate.
3. method as claimed in claim 1 or 2, wherein step 1 precipitation temperature is 60-90 ℃; The pH value of precipitation reaction is 6.5-9.0; Ageing time is 0.5-2 hour.
4. method as claimed in claim 3, wherein step 1 precipitation temperature is 65-80 ℃; The pH value of precipitation reaction is 7.0-8.5; Ageing time is 0.75-1.5h.
5. the method as described in claim 1,2,4 any one, wherein step 2 precipitation temperature is 65-90 ℃; Precipitation reaction pH value is 6.5-9.0; Ageing time is 0.5-2 hour.
6. method as claimed in claim 5, wherein step 2 precipitation temperature is 70-80 ℃; Precipitation reaction pH value is 7.0-8.5; Ageing time is 0.75-1.5h.
7. the method as described in claim 1,2,4,6 any one, wherein in the process of slurry again of step 3 reaction paste, add amount that desalted water adds be filter cake volume 1-10 doubly, temperature is 60-90 ℃, the temperature of desalted water is 65-75 ℃; Starch again filter 23-5 time; Wherein impurity content is qualified refers to that in filter cake, Na ion concentration is down to below 0.01-0.001%.
8. method as claimed in claim 7, wherein starches filter 23 again, and impurity content is qualified refers to that in filter cake, Na ion concentration is down to below 0.001%.
9. as right, want the method as described in 1,2,4,6,8 any one, wherein the gap of the colloid mill of step 4 is 0.1-5mm, the amount that desalted water adds be filter cake volume 1-10 doubly.
10. as right is wanted the method as described in 9, wherein the gap of the colloid mill of step 4 is 0.1-1.0mm.
11. methods as described in claim 1,2,4,6,8,10 any one, wherein, in the spray-drying process of step 5, EAT is 180-280 ℃; Charging rate is 300-3000ml/h; In spray-drying process, the ratio of catalyst feed and water is 1:1-1:10.
12. methods as claimed in claim 11, wherein, in the spray-drying process of step 5, EAT is 210-250 ℃; Charging rate is 1000-1500ml/h; In spray-drying process, the ratio of catalyst feed and water is 1:3-1:6.
13. the method for claim 1, wherein the dry rear powder calcining heat of the spraying of step 6 is 290-350 ℃; Material calcination time is 3-6h.
14. methods as described in claim 1,2,4,6,8,10,12 any one, the atomic ratio of wherein said catalyst consists of Cu:Zn:Al=(4～8): (1～5): (0.5～3).
15. methods as claimed in claim 14, the atomic ratio of wherein said catalyst consists of Cu:Zn:Al=(5～7): (2～4): (1～2).
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| CN110876937B (en) * | 2018-09-06 | 2022-08-23 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing gamma-butyrolactone by maleic anhydride hydrogenation |
| CN111378511B (en) * | 2018-12-28 | 2021-05-04 | 中国石油化工股份有限公司 | Biomass microwave gasification utilization method and system |
| CN112138665B (en) * | 2020-10-21 | 2022-10-28 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1586718A (en) * | 2004-07-29 | 2005-03-02 | 复旦大学 | Nano carbon material modified copper base catalyst and its preparing method |
| CN102164671A (en) * | 2008-09-26 | 2011-08-24 | 三菱瓦斯化学株式会社 | Methanol dehydrogenation catalyst for producing methyl formate and method for producing methyl formate |
| CN102350360A (en) * | 2011-08-17 | 2012-02-15 | 中国石油化工集团公司 | Aldehyde gas phase hydrogenation catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1586718A (en) * | 2004-07-29 | 2005-03-02 | 复旦大学 | Nano carbon material modified copper base catalyst and its preparing method |
| CN102164671A (en) * | 2008-09-26 | 2011-08-24 | 三菱瓦斯化学株式会社 | Methanol dehydrogenation catalyst for producing methyl formate and method for producing methyl formate |
| CN102350360A (en) * | 2011-08-17 | 2012-02-15 | 中国石油化工集团公司 | Aldehyde gas phase hydrogenation catalyst and preparation method thereof |
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