CN102600847A

CN102600847A - Catalyst for use in synthesis of methyl formate and preparation method and application thereof

Info

Publication number: CN102600847A
Application number: CN2012100262255A
Authority: CN
Inventors: 李德宝; 陈从标; 肖勇
Original assignee: Shanxi Institute of Coal Chemistry of CAS
Current assignee: Shanxi Institute of Coal Chemistry of CAS
Priority date: 2012-01-19
Filing date: 2012-01-19
Publication date: 2012-07-25
Anticipated expiration: 2032-01-19
Also published as: CN102600847B

Abstract

A catalyst molar ratio composition for synthesizing methyl formate is Cu:Zr:K=1:0.3-12:0.1-6. The catalysts were prepared by precipitation method, co-impregnation method and stepwise impregnation method. The invention has the advantages of good stability and high methyl formate selectivity.

Description

A kind of catalyst of synthetic methyl formate and preparation method and application

Technical field

The present invention relates to a kind of catalyst and preparation method and application, is a kind of catalyst and preparation method and application of synthetic methyl formate specifically.

Technical background

Methyl formate is a kind of important chemical intermediate, is set out by methyl formate, can produce important chemical such as formic acid, formamide, dimethyl formamide, dimethyl carbonate, ethylene glycol.Often adopt the carbonylation of methanol route at present in the commercial production, but this method equipment investment is bigger, the feed purification cost is high, has the catalyst separation problem in the process, and formed organic salt residue treatment is with high costs.Chinese patent CN1064672C discloses a kind of continuous preparation method of methyl formate, is intended to reduce organic salt and generate through increasing reaction pressure and temperature, reduces the disposal cost of bottoms.But reaction pressure is up to hundreds of atmospheric pressure at this moment, and this will increase equipment investment and running cost undoubtedly.In addition; It is the exothermic reaction that receives thermodynamic limitation that carbonylation of methanol generates the methyl formate reaction; Be that kinetics and thermodynamics are conflicting---need to improve reaction temperature to increase reaction rate from dynamics; Can impel chemical balance to be moved to the left and increase temperature, promptly equilibrium conversion reduces.Therefore, space-time yield is restricted, the influence process economy.

It is simple that the methanol dehydrogenation legal system is equipped with the methyl formate technological process, easy and simple to handle, non-corrosiveness, and equipment investment is less, and by-product hydrogen is a production route with essential industry meaning.Though this route receives thermodynamic limitation equally, conversion per pass is lower, can improve space-time yield through the mode that increases liquid air speed and reaction temperature simultaneously.Patent US 4149009 method of the methanol dehydrogenation system methyl formate of copper-zirconium-zinc/copper-zirconium-zinc-aluminium catalysis disclosed.Patent US 4319037 discloses the method that a kind of copper-based material that promotes with IIIA or IVA family element is made the Preparation of Catalyst methyl formate.Patent US 4232171 also discloses a kind of method that adopts the reaction of Cu-contained catalyst catalysis methanol to generate methyl formate.But these patents need to introduce diluent gas in the practical implementation process, and this will significantly increase the process energy consumption.Simultaneously, when not being during as dilution property gas, also can reduce product H with hydrogen ₂Grade reduces, and further increases application cost.Again owing to the reaction of methanol dehydrogenation system methyl formate is reacted for thermodynamic limitation, as H with one of goal response product ₂Will influence reaction during for raw material and carry out to the right, influence methanol conversion.Patent RU 2185370, US 5194675, US 5144062 disclosed methanol vapor phase dehydrogenations prepare in the method for methyl formate and de-emphasize the effect of diluent gas, but have all related to the use of chromium-containing catalyst.Common chromium presoma trivalent chromium, Cr VI have serious carcinogenesis, and the chromate waste water that forms in this type of catalyst preparation process possibly cause serious environmental to pollute, therefore should not be as industrial catalyst, and scale preparation.The methanol dehydrogenation that patent EP 2329881 describes prepares in the method for methyl formate, no longer adopt the chromium auxiliary agent, and emphasical catalyst performance is good, especially has the copper-zinc-Al catalysts of good stability.But its disclosed stability test result shows that catalyst stability does not fundamentally improve, and catalyst activity is left back promptly the loss about 30% at 1000 hours, obviously can not satisfy in the commercial production requirement to catalyst life.

Summary of the invention

The purpose of this invention is to provide a kind of stablizing, the catalyst of the synthetic methyl formate that the methyl formate selectivity is high and preparation method and application.

Catalyst molar ratio of the present invention consists of:

Cu∶Zr∶K＝1∶0.3-12∶0.1-6。

Preparation method of the present invention has two kinds.

Method one, the sedimentation type preparation method:

(1) configuration copper, zirconium soluble-salt solution obtain the copper zirconium solution, and are 0.01-4.0 in organic acid and copper ion trial sale ratio: 1 ratio is added organic acid in the copper zirconium solution, form solution A;

(2) make solution A and alkaline precipitating agent solution reaction, thereby copper, zirconium are precipitated out;

(3) sediment that filters repeatedly, obtains in the washing step (2) is removed the solubility heteroion;

(4) drying steps (3) gained deposition, and, obtain copper, Zr mixed oxide 250-700 ℃ of (preferred 300-500 ℃) roasting down;

(5) copper, the Zr mixed oxide with sylvite and gained mixes stone roller, again 250-700 ℃ of (preferred 300-500 ℃) roasting down, thereby finally obtains sedimentation type copper-zirconium-potassium catalyst sample.

Method two, the support type preparation method:

With ZrO ₂Be carrier, adopt common dipping or step impregnation method to prepare loaded catalyst.

1, common dipping.

Adopt ZrO ₂Be carrier, incipient impregnation has added the mixed solution of organic acid soluble copper salt and potassium nitrate or potassium nitrite, and wherein organic acid and copper ion mol ratio are 0.01-4.0: 1; With the gained sample drying, and 250-700 ℃ of (preferred 300-500 ℃) roasting down, and then obtain final catalyst.

2, step impregnation.

(1) prepare potassium salt soln respectively and contain organic acid soluble copper salting liquid, organic acid and copper ion mol ratio are 0.01-3.0: 1;

(2) adopt incipient impregnation normal direction ZrO ₂Carrier loaded a kind of metal, soaked carrier be usually 250-700 ℃ of roasting, and preferred 300-500 ℃;

(3) set by step (2) method of describing is to the another kind of metal of gained sample load, and obtains finished catalyst after dry, the roasting.

Aforesaid alkaline precipitating agent is one or more in alkali hydroxide soln, carbonate solution, the alkali metal acetate.

Aforesaid alkali metal hydroxide is potassium hydroxide, NaOH.Carbonate is potash, sodium carbonate, saleratus, sodium acid carbonate, ammonium hydrogencarbonate.Alkali metal acetate is a potassium acetate, sodium acetate.

Aforesaid soluble copper salt is a copper nitrate, and the solubility zirconates is a zirconium oxychloride, zirconium nitrate, zirconyl nitrate etc.

Aforesaid organic acid is meant the water-soluble organic acid that contains 2-3 carboxyl functional group, like oxalic acid, citric acid, malonic acid etc.

Aforesaid copper-zirconium-potassium catalyst applications method is following:

Gaseous methanol gets into the dehydrogenation reactor that copper-zirconium-potassium catalyst is housed and carries out dehydrogenation reaction, generates methyl formate, hydrogen and comprises CO and a small amount of CO ₂And CH ₄Accessory substance, dehydrogenation reactor outlet crude product is realized gas-liquid separation through flash tank, forms gas phase and slightly produces with liquid phase, gas phase adopts ammonia method cold or that methyl alcohol absorbs further to remove slightly the coagulated component in the product of gas phase in ammonia cooler or methyl alcohol absorption tower, obtains H ₂Content>=90% do not coagulate tail gas, the output battery limit (BL) uses; The coagulated component that forms is separated through rectifying column with thick the producing of liquid phase, obtains formic ether product and unreacted methanol, and unreacted methanol is returned dehydrogenation reactor as raw material after vaporizing.

Adopt aforesaid application process to carry out methyl formate production, methyl formate selectivity >=90%, methyl alcohol conversion per pass >=32%.

The methanol dehydrogenation reaction condition is as stated:

(1) copper-zirconium-potassium catalyst reduction activation, at 100-400 ℃, pressure 0.1-10MPa, air speed 500-5000h ^-1Through the gas reduction activation of hydrogen or hydrogen, activation process finishes when beds is imported and exported hydrogen content and no longer changed under the condition.

(2) methanol dehydrogenation reaction, reaction temperature 200-500 ℃, preferred 230-350 ℃, reaction pressure is at 0.1-2.0MPa, preferred 0.5-0.8MPa, methanol steam air speed GHSV=550-8500h ^-1(methanol liquid air speed LHSV=1.0-15h ^-1).

Aforesaid flash tank is in 0.05-0.08MPa, 60-100 ℃ following continued operation;

When adopting the ammonia cold process to collect the coagulated component in the gas phase, ammonia cooler inlet air temperature degree is 25-45 ℃, and the temperature of working off one's feeling vent one's spleen is 4-10 ℃; When adopting the methyl alcohol absorption process to collect the coagulated component in the gained gas phase, adopt the operation of methyl alcohol absorption tower, the absorption tower temperature is 15-35 ℃, pressure 0.5-1.0Mpa, 0.5-50 second time of contact, methyl alcohol and inlet tower gas mol ratio are 0.05-0.3.

Rectifying column is from cat head extraction methyl formate as stated, and the tower still gets methyl alcohol, and the tower operating pressure is 0.01-0.05Mpa; Reflux ratio is 1-8: 1, and theoretical cam curve is 10-50.

The present invention is compared with prior art:

(1) be that the copper complex of part is a presoma with the organic acid, realize effective dispersion, the grappling of copper species and zirconio material, the gained catalyst is efficient, stablize.

(2) Preparation of Catalyst does not relate to pollution sources such as chromium, and process is green, environmental friendliness.

(3) the methyl formate production process is unique raw material with gaseous methanol, need not to introduce diluent gas, is implemented in high yield acquisition methyl formate under the gentle relatively condition.

(4) product only comprises methyl formate, H ₂Reach CO, CO ₂, CH ₄Etc. several kinds of gaseous by-products, only need adopt a liquid distillation process (separation between methyl formate and the unreacted methanol), separating step is simple, and flow process is short, energy consumption is low.

Description of drawings

Fig. 1 is a methyl formate synthesis process flow diagram according to the invention.

As shown in the figure: A-reactor B-flash tank

C-ammonia cooler or methyl alcohol absorption tower D-rectifying column

1-gaseous methanol 2-reactor outlet crude product

The 3-gas phase is slightly produced the 4-liquid phase and is slightly produced

The methanol solution 6-that 5-can coagulate component or methyl formate does not coagulate tail gas

7-methyl formate 8-unreacted methanol.

The specific embodiment

Provide several illustrative rather than restrictive example below:

Embodiment 1:

(1) catalyst preparation process: take by weighing copper nitrate 4.0kg, zirconium oxychloride 64.02kg respectively, promptly Cu/Zr=1/12 (mol ratio) disposes mixing salt solution, and in mixed solution, adds oxalic acid in the ratio of oxalic acid: copper nitrate=0.01mol/mol, mixes.With potassium hydroxide is precipitating reagent, under 70 ℃, stirring condition, and with mixed solution mixed precipitation, aging then 1h.Repeatedly, the filtration washing gained precipitates removal solubility heteroion.With 60 ℃ of dry 48h of gained filter cake, and at 700 ℃ of following roasting 1h.In the gained sample, add the 0.17kg saleratus, the careful grinding evenly obtains final catalyst again behind 450 ℃ of following roasting 3hr.Catalyst is formed (mol ratio): Cu/Zr/K=1/12/0.1.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 8kg in the fixed bed reactors.Catalyst is earlier at 10.0MPa, 1000h ^-1, activation under 100 ℃, pure hydrogen atmosphere, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 0.1MPa, temperature is adjusted into 200 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=1.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.01MPa, 60 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.The thick product of gained gas phase is cooled to 25 ℃ again and gets into ammonia coolers and further remove and can coagulate component, and the cold outlet temperature of ammonia forms H at 4 ℃ ₂Content is that 91% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 1.56Nm ³/ h, the output battery limit (BL) uses.It is 10 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 8 the condition in 0.01MPa, reflux ratio; From the formic ether product 1.76kg/h of cat head extraction 97%, isolated unreacted methanol (4.21kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 90.1%, methyl alcohol conversion per pass 32%.

The gained data are data under the limit, below each embodiment all like this.

Embodiment 2:

(1) catalyst preparation process: take by weighing copper nitrate 8.0kg, zirconium nitrate 3.37kg respectively; Be Cu/Zr=1/0.3 (mol ratio); Dispose mixing salt solution, and in mixed solution, add citric acid, mix in the ratio of citric acid: copper nitrate=4.0mol/mol.With potash is precipitating reagent, under 60 ℃, stirring condition, and with mixed solution mixed precipitation, aging then 3h.Repeatedly, the filtration washing gained precipitates removal solubility heteroion.With 80 ℃ of dry 36h of gained filter cake, and at 250 ℃ of following roasting 8h.In the gained sample, add 13.73kg potash, the careful grinding evenly obtains final catalyst again behind 350 ℃ of following roasting 3hr.Catalyst is formed (mol ratio): Cu/Zr/K=1/0.3/6.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 6kg in the fixed bed reactors.Catalyst is earlier at 0.1MPa, 2000h ^-1, 400 ℃, contain 10%H ₂The hydrogen nitrogen mixed gas atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 2.0MPa, temperature is adjusted into 500 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=15.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.8MPa, 100 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.The thick product of gained gas phase is cooled to 45 ℃ of cold further removing of entering ammonia again can coagulate component, and the cold outlet temperature of ammonia forms H at 10 ℃ ₂Content is that 91.5% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 17.4Nm ³/ h, the output battery limit (BL) uses.It is 50 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 1 the condition in 0.05MPa, reflux ratio; From the formic ether product 19.95kg/h of cat head extraction 97%, isolated unreacted methanol (47.35kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 90.7%, the methyl alcohol conversion per pass is 32%.

Embodiment 3:

(1) catalyst preparation process: take by weighing copper nitrate 8kg, zirconyl nitrate 6.1kg respectively; Be Cu/Zr=1/0.8 (mol ratio); Dispose mixing salt solution, and in mixed solution, add malonic acid, mix in the ratio of malonic acid: copper nitrate=0.08mol/mol.With the ammonium hydrogencarbonate is precipitating reagent, under 80 ℃, stirring condition, and with mixed solution mixed precipitation, aging then 0.5h.Repeatedly, the filtration washing gained precipitates removal solubility heteroion.With the gained filter cake at 90 ℃ of dry 18h, and at 500 ℃ of following roasting 2h.In the gained sample, add 8.37kg potassium nitrate, the careful grinding evenly obtains final catalyst again behind 450 ℃ of following roasting 3hr.Catalyst is formed (mol ratio): Cu/Zr/K=1/0.8/5.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 7.0MPa, 500h ^-1, 250 ℃, contain 70%H ₂The hydrogen nitrogen mixed gas atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 0.5MPa, temperature is adjusted into 430 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=2.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.05MPa, 90 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.Gas phase is slightly produced and is got into the methyl alcohol absorption tower and further remove and can coagulate component, and the absorption tower is 15 ℃, 0.5Mpa operation down, methyl alcohol and the mol ratio of advancing tower gas are 0.05, time of contact 0.5s, then at cat head formation H ₂Content is that 91.2% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 4.61Nm ³/ h, the output battery limit (BL) uses.It is 20 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 5 the condition in 0.04MPa, reflux ratio; From the formic ether product 5.24kg/h of cat head extraction 97%, isolated unreacted methanol (9.53kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 90.4%, the methyl alcohol conversion per pass is 38%.

Embodiment 4:

(1) catalyst preparation process: take by weighing copper nitrate 8.0kg, zirconium oxychloride 12.8kg respectively, promptly Cu/Zr=1/1.2 (mol ratio) disposes solution respectively.And in copper nitrate solution, add oxalic acid in the ratio of oxalic acid: copper nitrate=3.0mol/mol, mix.With sodium carbonate is precipitating reagent, under 50 ℃, stirring condition, and with zirconyl chloride solution mixed precipitation, aging then 1.5h.Filter, wash once, the making beating of gained filter cake.Be precipitating reagent with sodium carbonate still, in the gained slurry, precipitate copper nitrate, the aging 3h of gained deposition.Repeatedly, the filtration washing gained precipitates removal solubility heteroion.With the gained filter cake at 90 ℃ of dry 18h, and at 500 ℃ of following roasting 2h.In the gained sample, add the 13.26kg saleratus, the careful grinding evenly obtains final catalyst again behind 300 ℃ of following roasting 4h.Catalyst is formed (mol ratio): Cu/Zr/K=1/1.2/4.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 0.5MPa, 5000h ^-1, 250 ℃, contain 50%H ₂Hydrogen-argon-mixed atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 0.8MPa, temperature is adjusted into 280 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=3.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.08MPa, 75 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.Gas phase is slightly produced and is got into the methyl alcohol absorption tower and further remove and can coagulate component, and the absorption tower is 35 ℃, 1.0Mpa operation down, methyl alcohol and the mol ratio of advancing tower gas are 0.3, time of contact 10.0s, then at cat head formation H ₂Content is that 96% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 11.42Nm ³/ h, the output battery limit (BL) uses.It is 30 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 7 the condition in 0.03MPa, reflux ratio; From the formic ether product 8.12kg/h of cat head extraction 97%, isolated unreacted methanol (14.52kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 95.8%, the methyl alcohol conversion per pass is 37%.

Embodiment 5:

(1) catalyst preparation process: take by weighing copper nitrate 10kg, zirconium nitrate 49.14kg respectively; Be Cu/Zr=1/3.5 (mol ratio); Dispose mixing salt solution, and in mixed solution, add citric acid, mix in the ratio of citric acid: copper nitrate=2.5mol/mol.With the potassium bicarbonate solution is precipitating reagent, under 80 ℃, stirring condition, and with mixed solution mixed precipitation, aging then 3.5h.Repeatedly, the filtration washing gained precipitates removal solubility heteroion.With the gained filter cake at 120 ℃ of dry 20h, and at 350 ℃ of following roasting 4h.In the gained sample, add the 12.19kg potassium acetate, the careful grinding evenly obtains final catalyst again behind 550 ℃ of following roasting 2hr.Catalyst is formed (mol ratio): Cu/Zr/K=1/3.5/3.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 15kg in the fixed bed reactors.Catalyst is earlier at 4.0MPa, 4000h ^-1, 300 ℃, contain 50%H ₂Hydrogen helium gas mixture atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 1.8MPa, temperature is adjusted into 315 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=4.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.8MPa, 85 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.The thick product of gained gas phase is cooled to 30 ℃ of cold further removing of entering ammonia again can coagulate component, and the cold outlet temperature of ammonia forms H at 10 ℃ ₂Content is that 91.8% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 12.65Nm ³/ h, the output battery limit (BL) uses.It is 40 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 2 the condition in 0.01MPa, reflux ratio; From the formic ether product 14.6kg/h of cat head extraction 97%, isolated unreacted methanol (30.08kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 91.1%, the methyl alcohol conversion per pass is 35%.

Embodiment 6:

(1) catalyst preparation process: take by weighing Schweinfurt green 6.0kg, zirconyl nitrate 49.64kg respectively, promptly Cu/Zr=1/6.5 (mol ratio) disposes mixing salt solution, and in mixed solution, adds oxalic acid in the ratio of oxalic acid: Schweinfurt green=2.5mol/mol, mixes.With the sodium acid carbonate is precipitating reagent, under 45 ℃, stirring condition, and with mixed solution mixed precipitation, aging then 3.5h.Filter, wash the gained deposition repeatedly, remove the solubility heteroion.With the gained filter cake at 110 ℃ of dry 24h, and at 450 ℃ of following roasting 3h.In the gained sample, add 4.56kg potash, the careful grinding evenly obtains final catalyst again behind 450 ℃ of following roasting 3hr.Catalyst is formed (mol ratio): Cu/Zr/K=1/6.5/2.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 0.6MPa, 3000h ^-1, activation under 400 ℃, pure hydrogen atmosphere, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 0.6MPa, temperature is adjusted into 480 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=10.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.4MPa, 100 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.The thick product of gained gas phase is cooled to 28 ℃ of cold further removing of entering ammonia again can coagulate component, and the cold outlet temperature of ammonia forms H at 8 ℃ ₂Content is that 92% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 23.44Nm ³/ h, the output battery limit (BL) uses.It is 25 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 6 the condition in 0.01MPa, reflux ratio; From the formic ether product 27.19kg/h of cat head extraction 97%, isolated unreacted methanol (46.83kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 91.3%, the methyl alcohol conversion per pass is 39%.

Embodiment 7:

(1) catalyst preparation process: take by weighing Schweinfurt green 2.0kg, zirconium oxychloride 29.8kg respectively; Be Cu/Zr=1/8.4 (mol ratio); Dispose mixing salt solution, and in mixed solution, add malonic acid, mix in the ratio of malonic acid: Schweinfurt green=1.6mol/mol.With NaOH, potassium hydroxide mixed solution is precipitating reagent, under 60 ℃, stirring condition, and with mixed solution mixed precipitation, aging then 10.0h.Filter, wash the gained deposition repeatedly, remove the solubility heteroion.With the gained filter cake at 60 ℃ of dry 72h, and at 650 ℃ of following roasting 1h.In the gained sample, add the 0.94kg potassium nitrite, the careful grinding evenly obtains final catalyst again behind 450 ℃ of following roasting 3hr.Catalyst is formed (mol ratio): Cu/Zr/K=1/8.4/1.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 1.2MPa, 2000h ^-1, 350 ℃, contain 30%H ₂Hydrogen helium gas mixture atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 1.2MPa, temperature is adjusted into 350 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=6.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.02MPa, 65 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.Gas phase is slightly produced and is got into the methyl alcohol absorption tower and further remove and can coagulate component, and the absorption tower is 25 ℃, 0.8Mpa operation down, methyl alcohol and the mol ratio of advancing tower gas are 0.1, time of contact 1.0s, then at cat head formation H ₂Content is that 92% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 12.26Nm ³/ h, the output battery limit (BL) uses.It is 35 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 3 the condition in 0.02MPa, reflux ratio; From the formic ether product 14.22kg/h of cat head extraction 97%, isolated unreacted methanol (30.57kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 91.3%, the methyl alcohol conversion per pass is 34%.

Embodiment 8:

(1) catalyst preparation process: take by weighing copper nitrate 9.0kg, zirconium nitrate 12.64kg respectively, promptly Cu/Zr=1/1 (mol ratio) disposes mixing salt solution, and in mixed solution, adds citric acid in the ratio of citric acid: copper nitrate=1.6mol/mol, mixes.With the liquor kalii acetici is precipitating reagent, under 60 ℃, stirring condition, and with mixed solution mixed precipitation, aging then 5.0h.Repeatedly, the filtration washing gained precipitates removal solubility heteroion.With the gained filter cake at 120 ℃ of dry 8h, and at 400 ℃ of following roasting 3h.In the gained sample, add 1.88kg potassium nitrate, the careful grinding evenly obtains final catalyst again behind 650 ℃ of following roasting 0.5hr.Catalyst is formed (mol ratio): ℃ u/Zr/K=1.0/1.0/1.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 0.1MPa, 1000h ^-1, 300 ℃, contain 30%H ₂The hydrogen nitrogen mixed gas atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 0.5MPa, temperature is adjusted into 280 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=2.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.01MPa, 100 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.The thick product of gained gas phase is cooled to 28 ℃ of cold further removing of entering ammonia again can coagulate component, and the cold outlet temperature of ammonia forms H at 5 ℃ ₂Content is that 97% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 4.33Nm ³/ h, the output battery limit (BL) uses.It is 45 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 1 the condition in 0.03MPa, reflux ratio; From the formic ether product 5.62kg/h of cat head extraction 97%, isolated unreacted methanol (9.51kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 96.9%, the methyl alcohol conversion per pass is 38%.

Embodiment 9:

(1) catalyst preparation process: the ZrO that takes by weighing 21.62kg ₂, take by weighing 4.0kg copper nitrate and 0.67kg potassium nitrate respectively, dispose nitrate solution respectively.Ratio in citric acid: copper nitrate=1.2mol/mol adds citric acid in nitrate solution, mix.The method of pressing incipient impregnation is to ZrO ₂Copper loaded, through 100 ℃ of dry 14h, and at 350 ℃ of following roasting 3h.The method of pressing incipient impregnation again is to gained sample load potassium, through 110 ℃ of dry 18h, and obtains final catalyst at 650 ℃ of following roasting 0.5h.Catalyst is formed (mol ratio): Cu/Zr/K=1/10.6/0.8.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 5.0MPa, 1000h ^-1, 300 ℃, contain activation under the pure hydrogen atmosphere, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 1.0MPa, temperature is adjusted into 380 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=8.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.03MPa, 85 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.The thick product of gained gas phase is cooled to 38 ℃ of cold further removing of entering ammonia again can coagulate component, and the cold outlet temperature of ammonia forms H at 6 ℃ ₂Content is that 93% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 15.69Nm ³/ h, the output battery limit (BL) uses.It is 18 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 2.5 the condition in 0.02MPa, reflux ratio; From the formic ether product 18.64kg/h of cat head extraction 97%, isolated unreacted methanol (41.41kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 92.5%, the methyl alcohol conversion per pass is 33%.

Example 10:

(1) catalyst preparation process: the ZrO that takes by weighing 21.62kg ₂, take by weighing 4.0kg copper nitrate and 5.64kg potassium nitrite, dispose mixing salt solution, and in mixed solution, add malonic acid in the ratio of malonic acid: copper nitrate=0.1mol/mol, mix.The method of pressing incipient impregnation is to ZrO ₂Copper loaded, potassium, through 120 ℃ of dry 24h, and at 700 ℃ of following roasting 1h.Obtaining catalyst composition (mol ratio) is: Cu/Zr/K=1/6.0/4.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 8kg in the fixed bed reactors.Catalyst is earlier at 2.0MPa, 2500h ^-1, 350 ℃, contain 25%H ₂Hydrogen-argon-mixed atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 0.5MPa, temperature is adjusted into 320 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=5.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.05MPa, 60 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.Gas phase is slightly produced and is got into the methyl alcohol absorption tower and further remove and can coagulate component, and the absorption tower is 30 ℃, 0.6Mpa operation down, methyl alcohol and the mol ratio of advancing tower gas are 0.08, time of contact 8.0s, then at cat head formation H ₂Content is that 94% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 8.0Nm ³/ h, the output battery limit (BL) uses.It is 15 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 4 the condition in 0.02MPa, reflux ratio; From the formic ether product 9.7kg/h of cat head extraction 97%, isolated unreacted methanol (20.37kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 93.6%, the methyl alcohol conversion per pass is 34%.

Embodiment 11:

(1) catalyst preparation process: the ZrO that takes by weighing 13.57kg ₂, take by weighing 8.0kg Schweinfurt green and 1.12kg potassium nitrite, dispose mixing salt solution, and in mixed solution, add citric acid in the ratio of citric acid: copper nitrate=1.8mol/mo1, mix.The method of pressing incipient impregnation is to ZrO ₂Copper loaded, potassium, through 90 ℃ of dry 24h, and at 350 ℃ of following roasting 5h.Obtaining catalyst composition (mol ratio) is: Cu/Zr/K=1/2.5/0.3.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 0.1MPa, 3500h ^-1, 380 ℃, contain 5%H ₂The hydrogen nitrogen mixed gas atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 0.6MPa, temperature is adjusted into 430 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=12.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.3MPa, 78 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.Gas phase is slightly produced and is got into the methyl alcohol absorption tower and further remove and can coagulate component, and the absorption tower is 28 ℃, 0.7Mpa operation down, methyl alcohol and the mol ratio of advancing tower gas are 0.2, time of contact 5.0s, then at cat head formation H ₂Content is that 93% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 28.54Nm ³/ h, the output battery limit (BL) uses.It is 30 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 3.5 the condition in 0.05MPa, reflux ratio; From the formic ether product 33.89kg/h of cat head extraction 97%, isolated unreacted methanol (55.18kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 92.5%, the methyl alcohol conversion per pass is 40%.

Embodiment 12:

(1) catalyst preparation process: the ZrO that takes by weighing 6.12kg ₂, take by weighing 4.0kg copper nitrate and 2.1kg potassium nitrate respectively, dispose nitrate solution respectively.Ratio in oxalic acid: copper nitrate=1.2mol/mol adds oxalic acid in copper nitrate solution, mix.The method of pressing incipient impregnation is to ZrO ₂Load potassium, through 110 ℃ of dry 36h, and at 450 ℃ of following roasting 3h.The method of pressing incipient impregnation again is to gained sample copper loaded, through 110 ℃ of dry 18h, and obtains final catalyst at 450 ℃ of following roasting 3h.Catalyst is formed (mol ratio): Cu/Zr/K=1/3.0/2.5.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 3.0MPa, 800h ^-1, 400 ℃, contain 75%H ₂The hydrogen nitrogen mixed gas atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 0.8MPa, temperature is adjusted into 300 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=6.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.08MPa, 65 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.The thick product of gained gas phase is cooled to 30 ℃ of cold further removing of entering ammonia again can coagulate component, and the cold outlet temperature of ammonia forms H at 10 ℃ ₂Content is that 98% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 12.86Nm ³/ h, the output battery limit (BL) uses.It is 20 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 5.5 the condition in 0.04MPa, reflux ratio; From the formic ether product 17.05kg/h of cat head extraction 97%, isolated unreacted methanol (28.53kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 98.0%, the methyl alcohol conversion per pass is 38%.

Embodiment 13:

(1) catalyst preparation process: the ZrO that takes by weighing 16.28kg ₂, take by weighing 6.0kg Schweinfurt green and 11.35kg potassium acetate respectively, dispose salting liquid respectively.Sour in malonic acid: the ratio of Schweinfurt green=1.2mol/mol adds malonic acid in Schweinfurt green solution, mix.The method of pressing incipient impregnation is to ZrO ₂Copper loaded, through 80 ℃ of dry 24h, and at 400 ℃ of following roasting 3h.The method of pressing incipient impregnation again is to gained sample load potassium, through 80 ℃ of dry 24h, and obtains final catalyst at 400 ℃ of following roasting 3h.Catalyst is formed (mol ratio): Cu/Zr/K=1/4.0/3.5.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 10kg in the fixed bed reactors.Catalyst is earlier at 8.0MPa, 3500h ^-1, activation under 180 ℃, pure hydrogen atmosphere, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 1.2MPa, temperature is adjusted into 265 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=3.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.4MPa, 80 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.The thick product of gained gas phase is cooled to 40 ℃ of cold further removing of entering ammonia again can coagulate component, and the cold outlet temperature of ammonia forms H at 7 ℃ ₂Content is that 96% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 5.88Nm ³/ h, the output battery limit (BL) uses.It is 26 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column 0.03MPa, reflux ratio are to operate under 2.0 the condition; From the formic ether product 7.46kg/h of cat head extraction 97%, isolated unreacted methanol (15.27kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 95.8%, the methyl alcohol conversion per pass is 34%.

Embodiment 14:

(1) catalyst preparation process: the ZrO that takes by weighing 7.34kg ₂, take by weighing 8.0kg copper nitrate and 2.29kg potash respectively, dispose salting liquid respectively.Ratio in citric acid: copper nitrate=1.2mol/mol adds citric acid in copper nitrate solution, mix.The method of pressing incipient impregnation is to ZrO ₂Copper loaded, through 60 ℃ of dry 72h, and at 600 ℃ of following roasting 1.5h.The method of pressing incipient impregnation again is to gained sample load potassium, through 120 ℃ of dry 12h, and obtains final catalyst at 400 ℃ of following roasting 3h.Catalyst is formed (mol ratio): Cu/Zr/K=1/1.8/1.0.

(2) the methanol dehydrogenation reaction generates methyl formate: behind above-mentioned gained shaping of catalyst, be seated in and carry out methanol dehydrogenation reaction, loaded catalyst 5kg in the fixed bed reactors.Catalyst is earlier at 0.3MPa, 1500h ^-1, 260 ℃, contain 95%H ₂The hydrogen nitrogen mixed gas atmosphere under activation, it is constant to import and export hydrogen content up to beds.After the activation, system pressure is adjusted into 1.7MPa, temperature is adjusted into 230 ℃, and the incision gaseous methanol contacts with copper-zirconium-potassium catalyst as stated and carries out methanol dehydrogenation and react LHSV=1.0h ^-1The reactor outlet crude product is realized gas-liquid separation through flash tank after 0.7MPa, 68 ℃ of following flash distillations, form gas phase and liquid phase and slightly produce.Gas phase is slightly produced and is got into the methyl alcohol absorption tower and further remove and can coagulate component, and the absorption tower is 18 ℃, 0.9Mpa operation down, methyl alcohol and the mol ratio of advancing tower gas are 0.06, time of contact 2.0s, then at cat head formation H ₂Content is that 93% (all the other are CO and a small amount of CO ₂And CH ₄Deng) do not coagulate tail gas 0.98Nm ³/ h, the output battery limit (BL) uses.It is 48 rectifying column rectifying that the coagulated component that forms gets into theoretical cam curve with the thick product of liquid phase; Rectifying column is to operate under 4.0 the condition in 0.02MPa, reflux ratio; From the formic ether product 1.16kg/h of cat head extraction 97%, isolated unreacted methanol (2.59kg/h) through the vaporization after as the raw material Returning reactor.Adopt described method to carry out methyl formate production, methyl formate selectivity 92.5%, the methyl alcohol conversion per pass is 33%.

Embodiment 15:

The evaluating catalyst long-term operation of embodiment 13 is to investigate copper-zirconium-potassium catalyst stability, and the gained result is as shown in table 1:

Table 1: copper-zirconium-potassium catalyst stability test

Line duration/hr	Methyl alcohol conversion per pass/%	Methyl formate selectivity/%
			24	38	96
120	35	97
			240	36	95
360	32	98
			528	35	94
840	31	97
			1272	34	96
2160	35	95

Claims

1. a catalyst for synthesizing methyl formate is characterized in that catalyst molar ratio consists of:

Cu:Zr:K=1:0.3-12:0.1-6.

2. the preparation method of the catalyst of a kind of synthetic methyl formate as claimed in claim 1, is characterized in that comprising the steps:

(1) Copper and zirconium soluble salt solutions are configured to obtain a copper-zirconium solution, and an organic acid is added to the copper-zirconium solution at a ratio of 0.01-4.0:1 to form a solution A;

(2) make solution A react with alkaline precipitant solution, thereby copper, zirconium are precipitated out;

(3) Repeatedly filter and wash the precipitate obtained in step (2) to remove soluble heteroions;

(4) drying the precipitate obtained in step (3), and roasting at 250-700° C. to obtain copper and zirconium mixed oxide;

(5) Mix and grind the potassium salt with the obtained mixed oxide of copper and zirconium, and then roast at 250-700° C., so as to finally obtain a precipitated copper-zirconium-potassium catalyst sample.

3. the preparation method of the catalyzer of a kind of synthetic methyl formate as claimed in claim 1, is characterized in that adopting _ZrO for carrier, equal volume impregnation has added the mixing of the soluble copper salt of organic acid and potassium nitrate or potassium nitrite solution, wherein the molar ratio of organic acid to copper ion is 0.01-4.0:1; the obtained sample is dried and calcined at 250-700° C. to obtain the final catalyst.

4. the preparation method of the catalyst of a kind of synthetic methyl formate as claimed in claim 1, is characterized in that comprising the steps:

(1) preparing potassium salt solution and soluble copper salt solution containing organic acid respectively, the molar ratio of organic acid and copper ion is 0.01-3.0: 1;

(2) Loading a metal on the _ZrO carrier by an equal-volume impregnation method, and the impregnated carrier is usually roasted at 250-700 ° C;

(3) Loading another metal on the obtained sample according to the method described in step (2), drying and calcining to obtain a finished catalyst.

5. the preparation method of the catalyst of a kind of synthetic methyl formate as claimed in claim 2 is characterized in that described alkaline precipitating agent is in alkali metal hydroxide solution, carbonate solution, alkali metal acetate one or more of.

6. the preparation method of the catalyst of a kind of synthetic methyl formate as claimed in claim 5 is characterized in that described alkali metal hydroxide is potassium hydroxide or sodium hydroxide.

7. the preparation method of the catalyst of a kind of synthetic methyl formate as claimed in claim 5 is characterized in that described carbonate is salt of wormwood, sodium carbonate, potassium bicarbonate, sodium bicarbonate or ammonium bicarbonate.

8. the preparation method of a kind of catalyst of synthesizing methyl formate as claimed in claim 5 is characterized in that described alkali metal acetate is potassium acetate or sodium acetate.

9. the preparation method of a kind of catalyst of synthesizing methyl formate as claimed in claim 2,3 or 4 is characterized in that described calcination temperature is 300-500 ℃.

10. as claimed in claim 2,3 or 4 described a kind of preparation method of the catalyst of synthetic methyl formate, it is characterized in that described soluble copper salt is copper nitrate.

11. the preparation method of the catalyst of a kind of synthetic methyl formate as claimed in claim 2 is characterized in that described soluble zirconium salt is zirconium oxychloride, zirconium nitrate or zirconyl nitrate.

12. as claimed in claim 2,3 or 4 described a kind of preparation method of the catalyst of synthesizing methyl formate, it is characterized in that described organic acid is the water-soluble organic acid containing 2-3 carboxyl functional groups.

13. the preparation method of the catalyst of a kind of synthetic methyl formate as claimed in claim 12 is characterized in that described water-soluble organic acid containing 2-3 carboxyl functional groups is oxalic acid, citric acid or, malonic acid.

14. the application of the catalyst of a kind of synthetic methyl formate as claimed in claim 1, is characterized in that comprising the steps:

Gaseous methanol enters the dehydrogenation reactor equipped with copper-zirconium-potassium catalyst for dehydrogenation reaction, generating methyl formate, hydrogen and its by-products including CO and a small amount of _CO2 and _CH4 , and the crude product at the outlet of the dehydrogenation reactor passes through The flash tank realizes gas-liquid separation to form gas phase and liquid phase crude product. The gas phase adopts ammonia cooling or methanol absorption method in the ammonia cooler or methanol absorption tower to further remove the condensable components in the gas phase crude product to obtain H ₂ The non-condensable tail gas with a content ≥90% is used in the output boundary area; the formed condensable components are separated from the liquid phase crude product through the rectification tower to obtain methyl formate product and unreacted methanol, and the unreacted methanol is vaporized Return to the dehydrogenation reactor as raw material.

15. the application of the catalyst of a kind of synthetic methyl formate as claimed in claim 14, it is characterized in that described methyl alcohol dehydrogenation reaction condition is:

(1) Reduction activation of copper-zirconium-potassium catalyst, at 100-400°C, pressure 0.1-10MPa, space velocity 500-5000h ^-1 , hydrogen or hydrogen-containing gas reduction activation, hydrogen content at the inlet and outlet of the catalyst bed The activation process ends when there is no more change;

(2) Methanol dehydrogenation reaction, reaction temperature 200-500°C, preferably 230-350°C, reaction pressure 0.1-2.0MPa, preferably 0.5-0.8MPa, methanol liquid space velocity LHSV=1.0-15h ^-1 .

16. the application of a kind of catalyst of synthesizing methyl formate as claimed in claim 15 is characterized in that in described step (2), reaction temperature is preferably 230-350 ℃, and reaction pressure is at 0.5-0.8MPa.

17. the application of a kind of catalyst of synthesizing methyl formate as claimed in claim 14 is characterized in that described flash tank operates continuously at 0.05-0.08MPa, 60-100 ℃.

18. the application of a kind of catalyst of synthesizing methyl formate as claimed in claim 14 is characterized in that when adopting the ammonia cooling method to collect the condensable components in the gas phase, the inlet gas temperature of the ammonia cooler is 25-45 ℃, The outlet gas temperature is 4-10°C; when the condensable components in the obtained gas phase are collected by the methanol absorption method, the methanol absorption tower is used for operation, the absorption tower temperature is 15-35°C, the pressure is 0.5-1.0Mpa, and the contact time is 0.5- 50 seconds, the molar ratio of methanol to tower gas is 0.05-0.3.

19. the application of a kind of catalyst of synthesizing methyl formate as claimed in claim 14 is characterized in that described rectifying tower is extracted methyl formate from tower top, tower still gets methyl alcohol, and tower operating pressure is 0.01-0.05 Mpa; the reflux ratio is 1-8:1, and the number of theoretical plates is 10-50.