CN1207957A

CN1207957A - Catalyst for synthesizing methyl mercaptan from synthesized gas contg. hydrogen sulfide

Info

Publication number: CN1207957A
Application number: CN 98118186
Authority: CN
Inventors: 杨意泉; 戴深峻; 林仁存; 张鸿斌
Original assignee: Xiamen University
Current assignee: Evonik Operations GmbH
Priority date: 1998-09-10
Filing date: 1998-09-10
Publication date: 1999-02-17
Anticipated expiration: 2018-09-10
Also published as: CN1072522C

Abstract

The catalyst has one carrier selected from SiO2, gamma-Al2O3, TiO2 or RE oxide and its active component Mo-S-K radical is transformed from precursor K2MoS4 or (NH4)MoS4+K2CO3. Under the conditions of 295 deg.c temperature, normal pressure, volume proportion of high-sulphur synthesis gas CO-H2-H2S being 1 to 2 to 0.1-1, and 2000-5000/hr space velocity, the catalyst can result in methyl mercaptan space-time yield of 0.15g/hr each gram of catalyst and selectivity of 98.5%.

Description

A kind of catalyzer by hydrogen sulfide containing synthetic gas synthesis of methyl mercaptan

The present invention relates to a kind of being used for to contain high H ₂Synthetic gas (the CO+H of S concentration ₂) be raw material, single stage method synthesis of methyl mercaptan (CH ₃SH) catalyzer and preparation method thereof.

Thiomethyl alcohol is synthetic egg amino acid, the important industrial chemicals of medicine and agricultural chemicals, and its classical production process is formed by potassium bisulfide and methine halide effect.The exploitation of other synthetic route was arranged again afterwards successively, U.S. Pat app1.856 for example, 232, a kind of method of making thiomethyl alcohol with hydrogen sulfide and methyl alcohol or ether reaction is disclosed; French Patent FR app1.93,112,491 to disclose a kind of be catalyzer with the transition metal, the method for dimethyl sulfide hydrogenation system thiomethyl alcohol; European patent EP 167,354 discloses a kind ofly makes carrier with titanium oxide, and nickel oxide or tantalum oxide are active ingredient, is the method that raw material is made thiomethyl alcohol with hydrogen sulfide and carbon monoxide.

The objective of the invention is to develop a kind of being used for to contain high H ₂Synthetic gas (the CO+H of S concentration ₂) be raw material, single stage method synthesis of methyl mercaptan (CH ₃SH) catalyzer.

Catalyzer of the present invention comprises carrier and active ingredient, and carrier is selected from silicon-dioxide (SiO ₂), activated alumina, especially γ-Al ₂O ₃, titanium oxide (TiO ₂) or rare earth oxide; Active ingredient Mo-S-K base can be selected from its presoma tetrathio potassium molybdate (K ₂MoS ₄) or tetrathio amine molybdate (NH ₄) ₂MoS ₄Add salt of wormwood (K ₂CO ₃); Catalyst system is expressed as the Mo-S-K/ carrier, and wherein the weight ratio of each component is: if active ingredient is with MoS ₂Meter, then MoS ₂/ carrier=(0.01～0.85)/1, preferably MoS ₂/ carrier=(0.1～0.6)/1

Take by weighing the presoma K of the Mo-S-K base of metering ₂MoS ₄, and it is dissolved in dimethyl formamide (DMF) solution, the consumption of DMF is controlled at can just be K ₂MoS ₄Dissolving fully, again with metering, selected carrier impregnation extracts DMF with anhydrous diethyl ether after leaving standstill 1h, promptly gets the catalyzer of Mo-S-K/ carrier after the vacuum-drying in argon gas (Ar) atmosphere in 300～400 ℃ of following calcination 2～4h.For using (NH ₄) ₂MoS ₄And K ₂CO ₃For Mo-S-K base presoma person, earlier K ₂CO ₃Be dissolved in an amount of distilled water, again with metering, selected carrier impregnation, then at 110 ℃ of oven dry 3h down, 550 ℃ of following calcination 4h take by weighing the (NH of metering again ₄) ₂MoS ₄, and it is dissolved in the DMF solution, the consumption of DMF is controlled at can just be (NH ₄) ₂MoS ₄Dissolving fully, the K that used load at last ₂CO ₃, and annealed carrier impregnation extracts DMF with anhydrous diethyl ether after leaving standstill 1h, promptly gets the catalyzer of Mo-S-K/ carrier after the vacuum-drying in argon gas (Ar) atmosphere in 400～450 ℃ of following calcination 2～4h.

Activity rating of catalyst carries out in fixed bed flowing reactive system, and the high-sulfur synthetic gas consists of CO/H ₂/ H ₂S=1/2/ (0.1～1), (V/V), 220～350 ℃ of temperature of reaction, pressure 0.2Mp, air speed (2～5) * 10 ³h ^-1, unstripped gas and product gc analysis.

The invention provides a kind of being used for to contain high H ₂The synthetic gas of S concentration is a raw material, and the Mo-S-K of single stage method synthesis of methyl mercaptan is catalyst based, and said catalyzer has very high activity to said reaction, and the selectivity that generates thiomethyl alcohol is up to 98.5%, and the space-time yield of thiomethyl alcohol is up to 0.15g/h.g _Cat

Further specify the present invention by embodiment below: example 1. takes by weighing 0.65g K ₂MoS ₄, be dissolved among the 3mL DMF, use 2g SiO ₂(80～100 order) dipping extracts DMF with anhydrous diethyl ether behind the 20min., is extracted totally until whole DMF, and then at 110 ℃ of following vacuum-drying 3h, in argon gas atmosphere, 350 ℃ of following calcination 4h obtain Mo-S-K/SiO at last again ₂Catalyzer, so the catalyst activity component Mo-S-K base of making is with MoS ₂The meter charge capacity is MoS ₂/ SiO ₂=0.28/1, (w/w), activity rating the results are shown in Table 1.Example 2～3 is K ₂MoS ₄Amount be adjusted into 1.3g and 1.95g respectively, other making method is with example 1, so activity of such catalysts component charge capacity is respectively 0.56/1,0.84/1, (w/w), activity rating the results are shown in Table 1.Example 4 takes by weighing 0.23g K ₂MoS ₄, be dissolved among the 2mL DMF, with 2g γ-Al ₂O ₃(40～60 order) dipping extracts DMF with anhydrous diethyl ether behind the 20min., is extracted totally until whole DMF, and then at 110 ℃ of following vacuum-drying 3h, in argon gas atmosphere, 350 ℃ of following calcination 4h obtain Mo-S-K/ γ-Al at last again ₂O ₃Catalyzer, so the catalyst activity component Mo-S-K base of making is with MoS ₂The meter charge capacity is MoS ₂/ γ-Al ₂O ₃=0.1/1, (w/w), activity rating the results are shown in Table 1.Example 5 takes by weighing 0.34g K ₂MoS ₄, be dissolved among the 2.5mL DMF, use 2g TiO ₂(40～60 order) dipping extracts DMF with anhydrous diethyl ether behind the 20min., is extracted totally until whole DMF, and then at 110 ℃ of following vacuum-drying 3h, in argon gas atmosphere, 350 ℃ of following calcination 4h obtain Mo-S-K/TiO at last again ₂Catalyzer, so the catalyst activity component Mo-S-K base of making is with MoS ₂The meter charge capacity is MoS ₂/ TiO ₂=0.15/1, (w/w), activity rating the results are shown in Table 1.Example 6 changes carrier into mishmetal (containing Ce 〉=85%) oxide compound, and all the other practices are with example 5, and so the catalyst activity component Mo-S-K base of making is with MoS ₂The meter charge capacity is MoS ₂/ mishmetal=0.15/1, (w/w), activity rating the results are shown in Table 1.

Table 1, the composition of example 1～6 catalyzer and activity rating result ^*

Embodiment	The catalyst activity component is (with MoS ₂Meter) charge capacity	Generate CH ₃SH selectivity (%)	CH ₃SH productive rate (g/hg _cat)
Embodiment		Generate CH ₃SH selectivity (%)	CH ₃SH productive rate (g/hg _cat)	???1	?MoS ₂/SiO ₂＝0.28/1	????97.1	????0.1
???2	?MoS ₂/SiO ₂＝0.56/1	????98.3	????0.14	???1	?MoS ₂/SiO ₂＝0.28/1	????97.1	????0.1
???2	?MoS ₂/SiO ₂＝0.56/1	????98.3	????0.14	???3	?MoS ₂/SiO ₂＝0.84/1	????98.5	????0.15
???4	?MoS ₂/γAl ₂O ₃＝0.1/1	????73.9	????0.07	???3	?MoS ₂/SiO ₂＝0.84/1	????98.5	????0.15
???4	?MoS ₂/γAl ₂O ₃＝0.1/1	????73.9	????0.07	???5	?MoS ₂/TiO ₂＝0.15/1	????94.1	????0.13
???6	?MoS ₂/ mishmetal=0.15/1	????90.5	????0.07	???5	?MoS ₂/TiO ₂＝0.15/1	????94.1	????0.13

^*Appreciation condition: the high-sulfur synthetic gas consists of CO/H ₂/ H ₂S=1/2/0.3 (V/V),

295 ℃ of temperature of reaction, pressure 0.2Mp, air speed 3 * 10 ³h ^-1Example 7. is K ₂CO ₃2.76g be dissolved in the 10mL distilled water, use 10g SiO again ₂Dipping 30min. is dried 3h down at 110 ℃ then, and 550 ℃ of following calcination 4h are standby, take by weighing (NH ₄) ₂MoS ₄5.16g, and be dissolved among the 15mL DMF K that used above-mentioned load again ₂CO ₃, and annealed SiO ₂Carrier impregnation extracts DMF with anhydrous diethyl ether after leaving standstill 1h, all is extracted totally until DMF, in vacuum drying oven 100 ℃ down behind the dry 3h again, promptly gets Mo-S-K/SiO in 450 ℃ of following calcination 4h in argon gas (Ar) atmosphere ₂Catalyzer, so (the Mo-S-K base is with MoS for the charge capacity of the catalyzer of making ₂Meter) be MoS ₂/ SiO ₂=0.51/1, (w/w); Consist of CO/H at the high-sulfur synthetic gas ₂/ H ₂S=1/2/0.3 (V/V), 295 ℃ of temperature of reaction, pressure is 0.2Mp, air speed 3 * 10 ³h ^-1Condition under carry out activity rating, the result generate thiomethyl alcohol selectivity 91%, the space-time yield 0.07g/hg of thiomethyl alcohol _Cat

Claims

1. the synthetic gas with high hydrogen sulfide concentration is a raw material, the catalyzer of single stage method synthesis of methyl mercaptan, said catalyzer is made up of active ingredient and carrier, it is characterized in that said active ingredient is the Mo-S-K based composition and use thereof in packaging, and the Mo-S-K based composition and use thereof in packaging in the said catalyzer is by presoma K ₂MoS ₄Or (NH ₄) ₂MoS ₄Add K ₂CO ₃Through load and calcination and get; Said carrier is a kind of SiO of being selected from ₂, activated alumina, TiO ₂Oxide compound or Ce content more than or equal to 85% mixed rare-earth oxide, the active ingredient Mo-S-K base in the said catalyzer is with MoS ₂Meter, the quantity of each composition is than being MoS ₂/ carrier=(0.01～0.80)/1, w/w.

2. produce the catalyzer of thiomethyl alcohol according to the said single stage method of claim 1, it is characterized in that the carrier activated alumina in the said catalyzer is γ-Al ₂O ₃

3. produce the catalyzer of thiomethyl alcohol according to the said single stage method of claim 1, it is characterized in that active ingredient Mo-S-K base in the said catalyzer is with MoS ₂Meter, the quantity of each composition is than being MoS ₂/ carrier=(0.1～0.6)/1, w/w.

4. make the method that the said single stage method of claim 1 is produced the thiomethyl alcohol catalyzer for one kind, it is characterized in that the presoma K of said catalyst activity component Mo-S-K base ₂MoS ₄Load be will the metering K ₂MoS ₄Be dissolved in dimethyl formamide (DMF) solution, the consumption of DMF is controlled at can just be K ₂MoS ₄Dissolving fully with the selected carrier impregnation of metering, extracts DMF with anhydrous diethyl ether after leaving standstill 1h then, after the vacuum-drying in argon gas (Ar) atmosphere in 300～400 ℃ of following calcination 2-4h; With (NH ₄) ₂MoS ₄And K ₂CO ₃During for presoma, earlier with the K that measures ₂CO ₃Be dissolved in an amount of distilled water, use selected carrier impregnation 30 minutes again, dry 3h down at 110 ℃ then, 550 ℃ of following calcination 4h are standby, will measure (NH ₄) ₂MoS ₄Be dissolved among the DMF, the consumption of DMF is controlled at can just be (NH ₄) ₂MoS ₄Fully the dissolving, the DMF solution of the presoma of gained again with the metering, said load K ₂CO ₃Carrier impregnation, extract DMF with anhydrous diethyl ether after leaving standstill 1h, after the vacuum-drying in argon gas (Ar) atmosphere in 400-450 ℃ of following calcination 2-4h.