CN109317216A

CN109317216A - The VHTi catalyst and preparation method of a kind of modification of solvent hot acid and application

Info

Publication number: CN109317216A
Application number: CN201811373819.7A
Authority: CN
Inventors: 程金燮; 王科; 陈鹏; 徐晓峰; 黄宏; 李倩; 张恒
Original assignee: Southwest Research and Desigin Institute of Chemical Industry
Current assignee: Southwest Research and Desigin Institute of Chemical Industry
Priority date: 2018-11-19
Filing date: 2018-11-19
Publication date: 2019-02-12
Anticipated expiration: 2038-11-19
Also published as: CN109317216B

Abstract

The invention discloses a kind of VHTi catalyst of solvent hot acid modification and preparation method and applications.The VHTi catalyst of acid modification is prepared using solvent thermal process, which is prepared by the raw material of following content component, and on the basis of the amount of Ti substance, V raw material accounts for the 5.0~64% of Ti, and acidic site H accounts for the 0.1~70% of Ti.The catalyst prepared using this method, acidic site is more evenly distributed, closer with carrier function, not easily runs off, promote the evenly dispersed of V species simultaneously, strengthen the synergistic effect of acidic site and redox position, made catalyst is high-efficient when being applied to one step of methanol and converting DMM processed, and Technical Economy is good, under mild reaction conditions, methanol conversion per pass height is up to high reachable 100%, the DMM one-way yield height of 80%, DMM selectivity up to 70%.In addition, easy, the with short production cycle, raw material of the present invention obtains convenient, soluble, treatment process has no irritating odor generation, and catalyst preparation each process easily realizes that industrialized production facilitates.

Description

The VHTi catalyst and preparation method of a kind of modification of solvent hot acid and application

Technical field

The preparation method for being related to a kind of sour modified catalyst the invention belongs to Material Field and the application in organic chemical industry, More particularly to a kind of VHTi catalyst using the modification of solvent thermal process acid and preparation method and in synthesis dimethoxymethane Application.

Background technique

Dimethoxymethane (DMM) molecular formula (CH₃O)₂CH₂Also known as dimethoxym ethane, it is a kind of widely used high added value Chemicals is used as chemical industry/medicine intermediate, green solvent, fuel and fuel additive.As chemical industry/medicine intermediate master It is used to produce diesel fuel additives polymethoxy dimethyl ether, pharmaceuticals industry chloromethyl ether, ethylene glycol intermediate product methoxyl group second Sour methyl esters, high-concentration formaldehyde, paraformaldehyde, polyformaldehyde, dimethyl carbonate, anion exchange resin and hydrogen；It is molten as green The toxic solvents such as the alternative benzene,toluene,xylene of agent are used for insecticide, colored ribbon, electronic equipment detergent, and substitution F11, F113 contain Chlorine solvent and freon make air freshener, leather polish, vehicle glazing agent, water paint solvent, for fragrance, makeup Product, drug, rubber, paint, ink product；Mainly make Methanol gasoline cosolvent and vapour/diesel oil as fuel and fuel additive Additive.About 30,000 yuan/ton of the market price domestic high concentration DMM, global production capacity is small, and advanced DMM production technology is with higher Application value.

Methanol is a kind of important basic chemical industry raw material.In the past 20 years, as country encourages the political affairs of coal chemical industry development Plan is put into effect, the rapid growth of methanol production capacity, current China's methanol production capacity or up to more than 8,100 ten thousand tons, yield or up to more than 4,200 ten thousand Ton.Since product development is inadequate downstream, there is serious excess capacity phenomenon in methanol industry.The inverted producible first contracting of methanol The higher chemicals of the added values such as aldehyde not only has economic significance, also helps and extends methanol industry chain, digests superfluous production capacity, Promote the sound development of coal chemical industry especially methanol industry.

The traditional handicraft of production DMM is that methanol first aoxidizes formaldehyde processed through Yin Fa or iron molybdenum method, and formaldehyde is again with methanol in acidity Under catalyst action condensation generate DMM, but the technique there are long flow path, consumption of raw materials with energy consumption is high, containing aldehyde/acid waste water is more, urges The problems such as agent severe corrosion to equipment and pollution products.One step of methanol is catalytically conveted to using oxidation-condensation coupling technique The new technology of DMM not only eliminates prepn. of formaldehyde by oxidation of methanol workshop section, and process shortens, and investment is reduced, and reduce waste water yield, It solves the problems, such as catalytic erosion equipment and polluted product, goes back by-product methyl formate, increase income.The key of the technology is asked Topic is the development of the bifunctional catalyst of oxidation-reduction quality and acid matched well, if catalyst redox is too weak, first The efficiency that alcohol is converted into formaldehyde will reduce, if too strong, be also easy to produce excessive oxidation product HCOOH, HCOOCH₃With CO_x；If acidity is too By force, methanol can Direct Dehydration generate dimethyl ether, if relatively too weak, intermediate product formaldehyde cannot completely and carbinol condensation, these are Decline DMM yield and the Technical Economy.

The modified means such as dipping, precipitating that mainly pass through of acid are carried out to catalyst at present to realize.Chinese patent CN101543775B discloses a kind of dipping Ti (SO₄)₂Solution is made with the acid VO with oxidisability_x/CeO₂-TiO₂Catalyst And its preparation method, one step of methanol is realized under lower temperature (120-200 DEG C) and is converted into DMM, but there are DMM selectivity (45- 90%) relatively low, stability is not good enough and preparation step mostly with control condition more than problem.Chinese patent CN101757906B is disclosed Contain SO with coprecipitation preparation₄ ^2-V-Ti-Al-O catalyst, although without with other means being introduced separately into SO₄ ^2-, seem letter Single, but practical preparation step is still more, the period is longer, and titanyl sulfate is tubing products, when containing the crystallization water solubility it is low, ammonium hydroxide Volatility and smell are larger, catalyst preparation more problems, are difficult to realize industry and generate, and in addition come from evaluation data, although urging Agent applied temps are lower, but there is a problem of that methanol conversion (27-39%) is relatively low.Chinese patent CN101757906B is disclosed A kind of V-Ti-M-S-O catalyst of coprecipitation preparation (M is Sr or Sb), although catalyst life is long, compares CN101757906B, preparation step is more, equally exists easy acquisition, dissolution and the environmental issue of part material, is making The DMM catalyst used time is taken, DMM selectivity (42.3-86.2%) is relatively low.Above-mentioned conventional sour modified method may cannot achieve acid Center and carrier, redox center it is stronger in conjunction with and cause to be lost, cannot achieve acidic site and redox position be good Synergistic effect, these cause the decline of catalyst activity, selectivity and stability.

Summary of the invention

The technical problems to be solved by the present invention are: in view of the above problems, providing a kind of simple and effective solvent The method of the modified VHTi catalyst of thermal process preparation acid can be oriented one step of methanol using the catalyst of this method preparation efficient It is converted into DMM, not only mild condition, low operation temperature, but also catalyst activity is high, the good, structure of selectivity and performance are stablized, tool There is good prospects for commercial application.

The technical solution adopted by the invention is as follows:

A kind of preparation method for the VHTi catalyst preparing acid modification using solvent thermal process, comprising the following steps:

S1, acid solution is prepared with nonaqueous solvents, to empty vectors TiO under solvent thermal process₂Or the TiO of load vanadium₂It carries out Modification；

S2, by S1 acid modification after empty vectors TiO₂Through filtering, drying, calcining, dipping vanadium solution, dried again VHTi catalyst is made in dry, calcining；Or the TiO for the load vanadium for modifying acid in S1₂Filtered, dry calcining be made VHTi urge Agent.

Further, when acid modifies blank TiO₂When carrier, comprising the following steps:

S1, compound concentration are not higher than 0.9mol/L acid solution, and TiO is added thereto₂, control acid solution and TiO₂Volume ratio Value 3~70 stirs 5~60min at -80~25 DEG C, 10~60r/min of mixing speed is controlled, by finely dispersed suspension It moves in solvent heat kettle, control packing density is not higher than 67%；

S2, above-mentioned solvent heat kettle is placed in 40~210 DEG C of baking ovens to processing 10~for 24 hours, again through the cooling suspension taken out It is filtered, obtained filter cake, again through 300~480 DEG C of 0.5~1.5h of calcining, obtains sour modification through 40~110 DEG C of 6~15h of drying TiO₂Carrier；

S3, the carrier that 10~50% ammonium metavanadate solution of mass fraction dipping S2 is obtained is prepared, is most dried afterwards through 25~120 DEG C Dry 12~for 24 hours, 380~550 DEG C of 1~2h of calcining obtain catalyst.

Further, in above-mentioned steps S1, acid solution and TiO₂Volume ratio be 5~45.

Further, when acid modifies the TiO of load vanadium₂When, comprising the following steps:

S1,10~50% ammonium metavanadate solution of mass fraction dipping TiO is prepared₂, the TiO₂Through 25~120 DEG C of drying 12~ For 24 hours, 380~550 DEG C of 1~2h of calcining obtain pre-catalyst；

S2, it prepares and is not higher than 0.9mol/L acid solution, be added the obtained pre-catalyst of S1 thereto, control acid solution and pre- Catalyst volume ratio 3~70 stirs 5~60min at -80~25 DEG C, controls 10~60r/min of mixing speed, will disperse Uniform suspension moves in solvent heat kettle, and control packing density is not higher than 67%；

S3, solvent heat kettle is placed in in 40~210 DEG C of baking ovens processing 10~for 24 hours, through the cooling suspension taken out using Filter, obtained filter cake, again through 300~480 DEG C of 0.5~1.5h of calcining, obtain catalyst through 40~110 DEG C of 6~15h of drying.

Further, in above-mentioned S2, the volume ratio of acid solution and pre-catalyst is 5~45.

Further, the solute of the acid solution be nitric acid, aluminum nitrate, hydrochloric acid, aluminium chloride, sulfuric acid, phosphoric acid, heteropoly acid, One of sulfonic acid is a variety of, and the solvent of the acid solution is ethyl alcohol, isopropanol, acetone, methyl acetate, one in ethyl acetate Kind is a variety of.Above-mentioned solute can be dissolved in above-mentioned organic solvent and obtain acid solution, be handled under solvent thermal process with this solution Carrier or catalyst can effectively modify its surface acidity.

Further, 50~160 DEG C of the water heating kettle treatment temperature, the type of cooling are natural cooling in an oven, take out It is forced in indoor cooling or cool water shower one of cooling or a variety of.

The invention also includes using VHTi catalyst made from aforementioned preparation process, the VHTi catalyst is by following content Prepared by the raw material of component, on the basis of the amount of Ti substance, V raw material accounts for the 5.0~64% of Ti, acidic site H account for Ti 0.1~ 70%, wherein the acidic site H is the acid group of sour solute.

Further, above-mentioned VHTi catalyst is prepared by the raw material of following content component, on the basis of the amount of Ti substance, V 9.0~45.0%, the H for accounting for Ti accounts for the 0.1~40.0% of Ti.

The method for being used to one step of methanol orientation converting dimethoxym ethane processed the invention also includes the VHTi catalyst of aforementioned preparation, Methanol through vaporization tower vaporization enters superheater with the air that preheated device preheats and mixed thermosetting superheated feedstock gas, controls first 0.1~3.5h of alcohol liquid hourly space velocity (LHSV)^-1, methanol and gaseous substance the ratio between amount (0.58~1.40): 1, superheated feedstock gas enters filling Converted in the reactor of VHTi catalyst, reactor be fixed bed or fluidized-bed reactor, control reactor batch temperature 80~ 250 DEG C, system pressure is not higher than 1.0MPa, and the crude product converted is separated up to dimethoxym ethane product.

Compared with prior art, the method have the advantages that:

1, the overcritical special operation condition with pressure that solvent generates under certain temperature in closed kettle makes to be dispersed therein Substance becomes vivaciously, modifies carrier or catalyst with this technique acid, and the acid site density for making absorption up is more reasonable, is distributed more equal It is even, it is closer with carrier or catalyst action, it is not easy to be lost during the reaction.

2, in addition, crystal habit, the grain size of object phase can be controlled when solvent thermal process prepares material by change condition With purity, the product of good dispersion is obtained, carrier is handled with this technique acid, it can be by adjusting raw material type and ratio, water heating kettle The structure and performance of packing density, treatment temperature and time and type of cooling control vector, secondary crystallization elimination carrier agglomeration, Make its more dispersed, partial size more evenly, while impurity is precipitated, improves Vector purity.Support surface acidity is improved with electrical, Further promote VO_xEvenly dispersed, the synergistic effect in reinforcing acid site and redox center of species, therefore made catalyst Use one step of methanol convert DMM processed when it is high-efficient, Technical Economy is good, 0.0~1.0MPa of pressure, 80~250 DEG C of temperature, 0.1~3.5h of liquid hourly space velocity (LHSV)^-1, n (alcohol): n (sky)=(0.58~1.40): under the conditions of 1 etc. is mild, methanol conversion per pass height can Up to high reachable 100%, the DMM one-way yield height of 80%, DMM selectivity up to 70%, catalyst activity is well excellent with selectivity.

3, it is solvent that the difference of solvent thermal process and hydrothermal process, which is that the former uses non-aqueous solvent organic matter, and the latter is with water For solvent, since organic matter boiling point, density and viscosity used are below water, solvent heat process conditions (temperature, solution and load Body or catalyst volume ratio, packing density, time, the type of cooling etc.) it is different from hydrothermal process, acidic aqueous is in viscosity, biography Advantage in terms of the physicochemical properties such as matter heat transfer efficiency make carrier or catalyst surface nature modification when be more quickly suitable for, can be more The duct for dredging carrier or catalyst well is distributed activated centre on its surface more uniform, matches corresponding treatment process, Solvent thermal process shows better effect compared to hydrothermal process when acid modifies VHTi catalyst.

4, the solvent thermal process relative ease time is short, and raw material obtains convenient, soluble, and treatment process has no irritating odor production Raw, catalyst preparation each process is easily realized, industrialized production is convenient.

Detailed description of the invention

Examples of the present invention will be described by way of reference to the accompanying drawings.Fig. 1 is catalyst in embodiment 1 and comparative example 1,2 XRD spectra.

Specific embodiment

All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive Feature and/or step other than, can be combined in any way.

Any feature disclosed in this specification unless specifically stated can be equivalent or with similar purpose by other Alternative features are replaced.That is, unless specifically stated, each feature is an example in a series of equivalent or similar characteristics ?.

Embodiment 1

The ethanol solution 591mL of 0.025mol/L benzene sulfonic acid is prepared, 59.9g TiO is added thereto₂, acid solution and TiO₂ Volume ratio about 38 stirs 5min at 20 DEG C, controls mixing speed 20r/min；The suspension for dispersing uniform is moved into solvent In hot kettle, control compactedness 20%, after kettle be placed in 110 DEG C of baking ovens handle 15h, taking-up is cooling with cooling water；It is suspended in kettle Liquid obtains acid modification TiO through filtering, 80 DEG C of drying 10h, 400 DEG C of calcining 1h₂Carrier；Prepare 11.98% metavanadic acid of mass fraction Ammonium salt solution takes the 73.23g solution to impregnate the carrier, most obtains catalyst through 60 DEG C of drying 18h, 500 DEG C of calcining 1h afterwards, wherein In terms of raw material, the amount 0.015mol of amount 0.075mol, the H substance of amount 0.75mol, the V substance of Ti substance.

By catalyst loaded in reactor, the methanol in vaporization tower vaporization enters superheater with the air in preheater preheating The unstripped gas of mixing overheat, overheat is converted into reactor catalysis, controls methanol liquid hourly space velocity (LHSV) 0.5h^-1, methanol and gaseous substance The ratio between amount 0.6:1,120 DEG C of bed temperature, system pressure 0.1MPa convert products obtained therefrom through gas chromatographic analysis.

Feed stock conversion, selectivity of product and yield is calculated as follows, evaluating catalyst result is listed in table 1.

Y_DMM=X_MeOH·S_DMM

Note: X_MeOH- methanol conversion；S_DMM- DMM selectivity；Y_DMM- DMM yield；n_MeOH,inThe object of methanol in-raw material The amount of matter；n_MeOH,outThe amount of methanol substance in-product；n_DMM,outThe amount of the substance of DMM in-product.

Embodiment 2

The ethanol solution 282mL of 0.43mol/L aluminum nitrate is prepared, 43.58g TiO is added thereto₂, acid solution and TiO₂ Volume ratio about 25 stirs 30min under 0 DEG C (with low-temperature cycling refrigerator temperature control), controls mixing speed 12r/min；It will divide It dissipates uniform suspension to move in solvent heat kettle, controls compactedness 40%, then kettle is placed in 80 DEG C of baking ovens and is handled for 24 hours, then Natural cooling in an oven；Suspension obtains acid modification TiO through filtering, 50 DEG C of drying 15h, 450 DEG C of calcining 0.5h in kettle₂It carries Body；It prepares 48.78% ammonium metavanadate solution 41.04g of mass fraction and impregnates the carrier, most forged afterwards through 110 DEG C of drying 12h, 450 DEG C It burns 1.5h and obtains catalyst, wherein in terms of raw material, the amount of amount 0.22mol, the H substance of amount 0.55mol, the V substance of Ti substance 0.36mol。

By catalyst loaded in reactor, the methanol in vaporization tower vaporization enters superheater with the air in preheater preheating Mixing overheat, the unstripped gas of overheat enter reactor catalysis conversion, control methanol liquid hourly space velocity (LHSV) 3.5h^-1, methanol and gaseous substance The ratio between amount 1.2:1,160 DEG C of bed temperature, system pressure 1.0MPa, convert products obtained therefrom through analytical calculation, evaluating catalyst As a result it is listed in table 1.

Embodiment 3

22.71% ammonium metavanadate solution 10.53g of mass fraction is prepared, 25.57g TiO is impregnated₂, then dried through 30 DEG C 22h, 400 DEG C of calcining 2.0h obtain pre-catalyst；The ethyl acetate solution 67mL for preparing 0.90mol/L sulfuric acid, is added thereto Pre-catalyst, acid solution and TiO₂Volume ratio about 9 stirs 60min under -60 DEG C (with low-temperature cycling refrigerator temperature control), control Mixing speed 45r/min processed；It will disperse uniform suspension to move in solvent heat kettle, control compactedness 60%, then kettle is placed in 10h is handled in 150 DEG C of baking ovens, then takes out the natural cooling in air；Suspension is through filtering, 85 DEG C of drying 6h, 300 DEG C in kettle Calcining 1.5h obtains catalyst, wherein in terms of raw material, the amount of amount 0.09mol, the H substance of amount 0.3mol, the V substance of Ti substance 0.06mol。

By catalyst loaded in reactor, the methanol in vaporization tower vaporization enters superheater with the air in preheater preheating Mixing overheat, the unstripped gas of overheat enter reactor catalysis conversion, control methanol liquid hourly space velocity (LHSV) 1.0h^-1, methanol and gaseous substance The ratio between amount 0.9:1,130 DEG C of bed temperature, system pressure 0.3MPa, convert products obtained therefrom through analytical calculation, evaluating catalyst As a result it is listed in table 1.

Comparative example 1

The aqueous solution 591mL of 0.025mol/L benzene sulfonic acid is prepared, 59.9g TiO is added thereto₂, control acid solution with TiO₂Volume ratio about 38 stirs 5min at 20 DEG C, controls mixing speed 20r/min；The suspension for dispersing uniform is moved to In water heating kettle, control compactedness 20%, after kettle be placed in 110 DEG C of baking ovens handle 15h, taking-up is cooling with cooling water；It is hanged in kettle Turbid obtains acid modification TiO through filtering, 80 DEG C of drying 10h, 400 DEG C of calcining 1h₂Carrier；Prepare the inclined vanadium of mass fraction 11.98% Acid ammonium solution takes the 73.23g solution to impregnate the carrier, most obtains catalyst through 60 DEG C of drying 18h, 500 DEG C of calcining 1h afterwards, In in terms of raw material, the amount 0.015mol of amount 0.075mol, the H substance of amount 0.75mol, the V substance of Ti substance.

By catalyst loaded in reactor, the methanol in vaporization tower vaporization enters superheater with the air in preheater preheating The unstripped gas of mixing overheat, overheat is converted into reactor catalysis, controls methanol liquid hourly space velocity (LHSV) 0.5h^-1, methanol and gaseous substance The ratio between amount 0.6:1,120 DEG C of bed temperature, system pressure 0.1MPa, conversion products obtained therefrom are calculated through gas chromatographic analysis, are catalyzed Agent evaluation result is listed in table 1.

Comparative example 2

The ethanol solution 591ml of 0.025mol/L benzene sulfonic acid is prepared, 59.9g TiO is added₂, it is dried at 80 DEG C 10h, then calcine 1h at 400 DEG C and obtain acid modification TiO₂Carrier prepares 11.98% ammonium metavanadate solution 73.23g of mass fraction The carrier is impregnated, most obtains catalyst through 60 DEG C of drying 18h, 500 DEG C of calcining 1h afterwards, wherein in terms of raw material, the amount of Ti substance The amount 0.015mol of amount 0.075mol, the H substance of 0.75mol, V substance.

By catalyst loaded in reactor, the methanol in vaporization tower vaporization enters superheater with the air in preheater preheating The unstripped gas of mixing overheat, overheat is converted into reactor catalysis, controls methanol liquid hourly space velocity (LHSV) 0.5h^-1, methanol and gaseous substance The ratio between amount 0.6:1,120 DEG C of bed temperature, system pressure 0.1MPa convert products obtained therefrom through gas chromatographic analysis, and catalyst is commented Valence result is listed in table 1.

1 embodiment 1-3 of table and comparative example 1,2 produce the catalytic performance of dimethoxym ethane

Embodiment	Methanol conversion per pass/%	Dimethoxym ethane selectivity/%	Dimethoxym ethane one-way yield/%
				Embodiment 1	59.63	100.00	59.63
Embodiment 2	76.81	85.23	65.47
				Embodiment 3	68.45	95.74	65.53
Comparative example 1	52.07	97.69	50.87
				Comparative example 2	26.19	89.03	23.32

Catalyst formulation, evaluation technique and preparation condition are all identical in embodiment 1 and comparative example 1,2, and difference is only that acid The technique of modified catalyst, embodiment 1 are modified with hydrothermal process acid and are catalyzed with solvent thermal process acid modified catalyst, comparative example 1 Agent, comparative example 2 is with infusion process acid modified catalyst.From 1 data of table it is found that in terms of methanol conversion per pass, embodiment 1 is more right Ratio 1,2 promotes 14.52%, 127.68% respectively；In terms of dimethoxym ethane selectivity, embodiment 1 is up to 100%, compared with comparative example 1,2 difference are high by 2.37%, 12.32%.Also, the dimethoxym ethane one-way yield that embodiment 1,2,3 obtains be above comparative example 1 (point Not high 17.22%, 28.70%, 28.82%), (high 155.70%, 180.75%, 181.00%) respectively of comparative example 2.This table It is bright: the work of catalyst can be promoted by a relatively large margin compared to hydrothermal process or the catalyst of infusion process preparation acid modification, solvent thermal process Property, improve selectivity to a certain extent.Due to the lower boiling point of organic solvent, viscosity, density and the spy in terms of mass-and heat-transfer Have the unique effect of attribute and solvent thermal process in terms of improving material physicochemical property, solvent thermal process in modification carrier or When catalyst surface property not only more rapidly and efficiently, but also keep acidic site, redox position and distribution of charges preferably, dredging On logical carrier or catalyst duct more fully thoroughly, therefore, catalyst conversion methanol is that the performance of dimethoxym ethane obtains further It is promoted.

As can be seen from Figure 1, obviously there is Detitanium-ore-type TiO in embodiment 1 and comparative example 1,2₂(PDF NO.21-1272: 25.3 °, 37.8 °, 48.1 °, 55.1 °, 62.8 °, 70.3 °, 75.1 °, 83.2 °) and V₂O₅(PDF NO.41-1426:20.2°、 26.1 °, 31.0 °, 32.4 °, 34.2 °, 41.2 °, 47.6 °, 52.0 °) characteristic diffraction peak.Benzene sulfonic acid is to TiO₂It is modified And evolution is decomposed after calcining, therefore have no its characteristic peak, shows that three kinds of techniques obtain the catalyst, but it has been observed that Embodiment 1 and comparative example 1,2 are in V₂O₅Peak shape, peak intensity, have difference in half-peak breadth, the former relatively after both peak shape more disperse, peak Intensity is lower, half-peak breadth is bigger, illustrates that the former has smaller V₂O₅Crystal grain, higher V₂O₅Dispersion degree, i.e., with solvent thermal process The VHTi catalyst of preparation has better active sites dispersibility compared with hydrothermal process and infusion process, and structure determines property, this is also Catalyst performance in embodiment 1 is better than one of the immanent cause of comparative example 1,2.

The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed New feature or any new combination, and disclose any new method or process the step of or any new combination.

Claims

1. a kind of method for preparing acid modification VHTi catalyst using solvent thermal process, which comprises the following steps:

S1, acid solution is prepared with nonaqueous solvents, to empty vectors TiO under solvent thermal process₂Or the TiO of load vanadium₂It is repaired Decorations；

S2, by S1 acid modification after empty vectors TiO₂Through filtering, drying, calcining, dipping vanadium solution, is dried, calcined again VHTi catalyst is made；Or the TiO for the load vanadium for modifying acid in S1₂It filtered, dry the obtained VHTi catalyst of calcining.

2. the method according to claim 1, wherein the following steps are included:

S1, compound concentration are not higher than 0.9mol/L acid solution, and TiO is added thereto₂, control acid solution and TiO₂Volume ratio 3~ 70,5~60min is stirred at -80~25 DEG C, is controlled 10~60r/min of mixing speed, finely dispersed suspension is moved to molten In the hot kettle of agent, control packing density is not higher than 67%；

S2, above-mentioned solvent heat kettle is placed in 40~210 DEG C of baking ovens to processing 10~for 24 hours, through the cooling suspension taken out using Filter, obtained filter cake, again through 300~480 DEG C of 0.5~1.5h of calcining, obtain acid modification through 40~110 DEG C of 6~15h of drying TiO₂Carrier；

S3, the carrier that 10~50% ammonium metavanadate solution of mass fraction dipping S2 is obtained is prepared, most afterwards through 25~120 DEG C of drying 12 ~for 24 hours, 380~550 DEG C of 1~2h of calcining obtain catalyst.

3. the method according to claim 1, wherein the following steps are included:

S1,10~50% ammonium metavanadate solution of mass fraction dipping TiO is prepared₂, soak vanadium after TiO₂Through 25~120 DEG C of drying 12 ~for 24 hours, 380~550 DEG C of 1~2h of calcining obtain pre-catalyst；

S2, it prepares not higher than 0.9mol/L acid solution, the pre-catalyst that S1 is obtained is added thereto, control acid solution is catalyzed with pre- Agent volume ratio 3~70 stirs 5~60min at -80~25 DEG C, controls 10~60r/min of mixing speed, will be uniformly dispersed Suspension move in solvent heat kettle, control packing density be not higher than 67%；

S3, solvent heat kettle is placed in in 40~210 DEG C of baking ovens processing 10~for 24 hours, through the cooling suspension taken out using filter, obtained The filter cake arrived, again through 300~480 DEG C of 0.5~1.5h of calcining, obtains catalyst through 40~110 DEG C of 6~15h of drying.

4. described in any item methods according to claim 1~3, which is characterized in that the solute of the acid solution is nitric acid, nitric acid One of aluminium, hydrochloric acid, aluminium chloride, sulfuric acid, phosphoric acid, heteropoly acid, organic sulfonic acid are a variety of, and the solvent of the acid solution is second One of alcohol, isopropanol, acetone, methyl acetate, ethyl acetate are a variety of.

5. according to the method described in claim 2, it is characterized in that, in the S1, acid solution and TiO₂Volume ratio be 5~ 45。

6. according to the method described in claim 3, it is characterized in that, in the S2, the volume ratio of acid solution and pre-catalyst It is 5~45.

7. according to the described in any item methods of claim 2,3,5,6, which is characterized in that the solvent heat kettle treatment temperature 50~ 160 DEG C, the type of cooling be in an oven natural cooling, take out in indoor cooling or cool water shower force it is one of cooling or It is a variety of.

8. modifying VHTi catalyst using acid made from any one of claim 1~7 preparation method, which is characterized in that institute VHTi catalyst is stated to be prepared by the raw material of following content component, on the basis of the amount of Ti substance, V raw material accounts for the 5.0~64% of Ti, Acidic site H accounts for the 0.1~70% of Ti, wherein the acidic site H is the acid group of sour solute.

9. VHTi catalyst according to claim 8, which is characterized in that the VHTi catalyst is by following content component Raw material preparation, on the basis of the wherein amount of Ti substance, 9.0~45.0%, the H that V accounts for Ti accounts for the 0.1~40.0% of Ti.

10. the method that the VHTi catalyst of claim 8 or 9 is used to one step of methanol orientation converting dimethoxym ethane processed, feature exist In the methanol of vaporization tower vaporization enters superheater with the air preheated in preheater and mixed thermosetting superheated feedstock gas, controls Methanol liquid hourly space velocity (LHSV) 0.1-3.5h^-1, methanol and gaseous substance the ratio between amount (0.58-1.40): 1, superheated feedstock gas enters filling It is converted in the reactor of VHTi catalyst, reactor is fixed bed or fluidized-bed reactor, controls reactor batch temperature 80- 250 DEG C, system pressure is not higher than 1.0MPa, and the crude product converted is separated up to dimethoxym ethane product.