CN102019183A

CN102019183A - Catalyst for producing hydrogen from hydrocarbon steam conversion or carboxyl syngas reaction and preparation method thereof

Info

Publication number: CN102019183A
Application number: CN2009100189741A
Authority: CN
Inventors: 王昊; 种道文; 姜建波; 尹长学; 程玉春
Original assignee: China Petroleum and Chemical Corp
Current assignee: China Petroleum and Chemical Corp
Priority date: 2009-09-22
Filing date: 2009-09-22
Publication date: 2011-04-20
Anticipated expiration: 2029-09-22
Also published as: CN102019183B

Abstract

The present invention relates to a catalyst particularly used for producing hydrogen from large energy-saving hydrocarbon steam conversion or carboxyl syngas reaction, and preparation method thereof. The catalyst takes nickel as an active component, rare earth as a promoter, alumina as a carrier, cement as an adhesive and aluminum nitrate as a modifier; The catalyst has excellent physicochemical properties, high mechanical strength, and high crushing strength of above 300 N/particle. The catalyst can be used with stable activity under conditions of high passageway temperature, high space velocity, high heat flux, and low water-carbon ratio; and the methane at the convertion exit meets the process requirements.

Description

Producing hydrogen from steam conversion of hydrocarbons or oxo-synthesis gas catalyst for reaction and preparation method thereof

Technical field

The present invention relates to a kind of large-scale energy-saving type hydrocarbon steam conversion that is used for and produce hydrogen or oxo-synthesis gas catalyst for reaction, this catalyst also can be used for the one-stage converter that hydrogen or oxo-synthesis gas technology are produced in other hydrocarbon steam conversion.

Background technology

In order to pursue maximum economic benefits, the economic scale of external oil refining apparatus is generally more than 15Mt/a.In order to adapt to contemporary oil refining enterprise to device for producing hydrogen high reliability, high flexibility, low cost, low consumption requirement, maximization hydrogen manufacturing has become a kind of trend, and single cover scale is 100,000Nm ³/ h or more than, reached 230 individually, 000Nm ³/ h.External hydrogen producing technology is compared with domestic hydrogen producing technology, and have following characteristics: (1) extensively adopts the pre-inversion technology; (2) process parameter optimizing, reburner operating parameter are compared with domestic technique and are shown as " three high one is low " (high gateway temperature, high-speed, high heat flux, low steam carbon ratio); (3) Jie Nengjianghao means are meticulousr.

Less with the hydrogen amount when China starts to walk owing to hydrogen manufacturing, the device for producing hydrogen scale is less relatively, and list overlaps the hydrogen manufacturing scale 60 at present, 000Nm ³Below/the h, generally 10,000～20,000Nm ³Between/the h.Compare with external maximization hydrogen producing technology, its gap shows: (1) does not adopt the pre-inversion technology; (2) technological parameter is owed to optimize, low gateway temperature, low-speed, low heat flux, high steam/hydrocarbons ratio; (3) Jie Nengjianghao means have gap, and energy consumption is higher.In in recent years, there have been six cover maximization water vapour reforming hydrogen manufacturing technology bags and supporting catalyst to introduce, hydrogen output reaches 552000Nm ³/ h, above-mentioned introduction maximization water vapour reforming hydrogen manufacturing device all adopts external import catalyst.

The naphtha steam reforming catalyst that patent CN89105205.4 introduces, commercial Application prove that it uses carbon space velocity＜800h-1, can't adapt to high carbon space velocity and transform.Other domestic catalyst is that resistance to carbon formation is strong as advantages such as Z402, Z417, and shortcoming is active low, uses carbon space velocity low, is not suitable for the low steam carbon ratio condition.The natural gas hydrogen preparation catalyst advantage that CN89106847 and CN961106077 introduce is active height, good hydrothermal stability, mechanical strength height, but anti-carbon nature can be not good under the low steam carbon ratio condition, use carbon space velocity also lower, also there is similar problem in other homemade natural gas hydrogen preparation catalyst.External catalyst, as the R67 of Tops φ e, R67-7H catalyst with MgAlO ₂Be carrier impregnation nickel active component, active high, adapt to high carbon space velocity and low steam carbon ratio condition, but have the high temperature hydration problems.

Through contrast, think that the requirement of existing catalyst and large-scale energy-saving process for making hydrogen also has a certain distance, researched and developed a kind of Hydrocarban coversion catalysts that is used for large-scale energy-saving process for making hydrogen or traditional producing hydrogen from steam conversion technology for this reason.

Summary of the invention

Technical problem to be solved by this invention provides a kind of producing hydrogen from steam conversion of hydrocarbons or oxo-synthesis gas catalyst for reaction and preparation method thereof, and catalyst has active height, good hydrothermal stability, the high carbon space velocity conversion of adaptation and low steam carbon ratio service condition.

A kind of producing hydrogen from steam conversion of hydrocarbons of the present invention or oxo-synthesis gas catalyst for reaction, comprise alumina support and nickel active component, it is characterized in that also containing in the catalyst oxide of promoter rare earth metal and/or the oxide and the modifier aluminum nitrate of alkaline-earth metal, alumina support is binding agent with cement, wherein nickel is counted 5～25% of catalyst quality with oxide, promoter is 0.5～20% of catalyst quality, modifier is 2～8% of catalyst quality, surplus is a carrier, contains the cement of 10～30% (accounting for the carrier quality) in the carrier.

Described promoter is preferably 8～16% of catalyst quality.

The method for preparing catalyst of the present invention, earlier with aluminium oxide and pore creating material, lubricant and binding agent cement mixing, mixed proportion was at 100: 1: 1: 30～100: 5: 5: 100, carry out ball milling then, mediate, granulation, extrusion modling, oven dry, roasting makes the presintering carrier, wherein sintering temperature is between 1100～1480 ℃, roasting time 2～6 hours, adopt the method for flooding altogether or flooding respectively flooding active component nickel on the presintering carrier then, modifier and promoter, dip time is 0.5～6 hour, after the oven dry, under 400～600 ℃ temperature, decomposed 1～6 hour, and then the repeated impregnations decomposition once, so just obtained reforming catalyst finished product of the present invention.

Wherein pore creating material can be graphite, stearic acid or stearates, nitric acid, γ-Al ₂O ₃, cellulose, string etc.Preferred graphite, string.

Lubricant can be graphite, stearic acid or stearates, nitric acid etc.Preferred graphite, stearic acid.

Reforming catalyst of the present invention has good physical and chemical performance, and mechanical strength is good, and the crushing strength of catalyst can reach more than 300N/.The catalyst carrier porosity is controlled at 20-24%, and greater than 300N/, radially breaking strength is greater than 450N/ to breaking strength in the hole.Be applicable to 630-650 ℃ of reburner inlet temperature, outlet temperature 850-890 ℃, transform carbon space velocity 1000～1400h ^-1, total steam/hydrocarbons ratio 2.5～2.75, pressure 2.0-4.0MPa 450-520 ℃ of large-scale energy-saving type process for making hydrogen conditioned disjunction reburner inlet temperature, outlet temperature 750-820 ℃, transform carbon space velocity＜900h ^-1, total steam/hydrocarbons ratio 2.8～3.2, pressure 2.0-4.0MPa 450-520 ℃ of traditional process for making hydrogen conditioned disjunction reburner inlet temperature, outlet temperature 700-820 ℃, transform carbon space velocity＜1900h ^-1, total steam/hydrocarbons ratio 2.0～2.8, the system ammonia of pressure 2.0-4.0MPa, system oxo-synthesis gas process conditions.This reforming catalyst can use under high gateway temperature, high-speed, high heat flux, low steam carbon ratio condition, and is activity stabilized, transforms outlet methane and satisfies technological requirement.

Description of drawings

Fig. 1 is common catalyst pressurization activity rating device schematic diagram;

Among the figure: the 1-oil-measuring pump; 2-water measuring pump; The 3-vaporizer; The 4-blender; The 5-tubular reactor; The 6-condenser; The 7-separator; The 8-voltage-stablizer; The 9-wet flow indicator

The specific embodiment

Below in conjunction with embodiment the present invention is described.

Embodiment 1:

The preparation of catalyst A:

With high-temperature calcination aluminium oxide 85kg, graphite 2kg, kapok 0.5kg, aluminous cement 12.5kg mixing and ball milling adds suitable quantity of water, mediates, and granulation is pressed into four hole special-shaped rings.Oven dry 1230～1250 ℃ of sintering temperatures 3 hours, promptly makes presintering carrier a.

Be configured to 100L solution with 109kg nickel nitrate, 1kg lanthanum nitrate, 1kg aluminum nitrate, above-mentioned carrier a is immersed in this solution, take out after 2 hours, decomposed 2 hours down at 400 ℃ 100 ℃ of oven dry 4 hours.This process of repetition once just makes catalyst A.Analyzing it consists of:

Component

NiO

La ₂O ₃

Al ₂O ₃

CaO

Content, %

12.0

1.53

Surplus

4.8

Catalyst A of the present invention and industrial catalyst C are compared condition evaluating, the results are shown in following table.

Catalyst A and industrial catalyst C condition test result

Can see that in the pressure test process of contrast industrial catalyst C, transform in the outlet process gas has C always ₂Exist.Even catalyst A C do not occur yet in the reformed gas when high carbon space velocity condition test ₂In whole pressure condition process of the test, never have C in the reformed gas ₂And industrial catalyst C can't finish high carbon space velocity condition test smoothly.This industrial catalyst C that proves absolutely A catalyst comparison ratio has more good activity of conversion, anti-carbon ability and stronger adaptive capacity.

Catalyst A of the present invention and catalyst C are carried out high temperature contrast condition evaluating, the results are shown in following table.Catalyst A and catalyst C hot conditions result of the test

The hot conditions result of the test shows that the A catalyst can be applicable to the higher temperature condition.By the hot conditions verification experimental verification A catalyst performance be better than comparative catalyst C.

Embodiment 2

The preparation of catalyst B:

With high-temperature calcination aluminium oxide 92kg, CaCO ₃5kg, CaO 3kg, graphite 2kg, kapok 0.5kg mixing and ball milling adds suitable quantity of water, mediates, and extrusion modling makes seven muscle Wheel ring packings.Oven dry was burnt 3 hours under 1200～1250 ℃ of temperature, promptly made presintering carrier b.

The inventory of maceration extract and dipping process and catalyst A in full accord makes catalyst B.Analyzing it consists of:

Component	NiO	La ₂O ₃	Al ₂O ₃	CaO
					Content, %	12.0	1.49	Surplus	5.1

Catalyst B is carried out the high temperature comparative evaluation, the results are shown in following table.

Catalyst A and catalyst B hot conditions result of the test

As can be seen, the performance of catalyst B and catalyst A is close.

Claims

1. producing hydrogen from steam conversion of hydrocarbons or oxo-synthesis gas catalyst for reaction, comprise alumina support and nickel active component, it is characterized in that also containing in the catalyst oxide of promoter rare earth metal and/or the oxide and the modifier aluminum nitrate of alkaline-earth metal, alumina support is binding agent with cement, wherein nickel is counted 5～25% of catalyst quality with oxide, promoter is 0.5～20% of catalyst quality, modifier is 2～8% of catalyst quality, surplus is a carrier, contains the cement of 10～30wt% in the carrier.

2. catalyst according to claim 1 is characterized in that described promoter is 8～16% of catalyst quality.

3. method for preparing the described catalyst of claim 1, it is characterized in that earlier aluminium oxide and pore creating material, lubricant and binding agent cement mixing, mixed proportion was at 100: 1: 1: 30～100: 5: 5: 100, carry out ball milling then, mediate, granulation, extrusion modling, oven dry, roasting makes the presintering carrier, wherein sintering temperature is between 1100～1480 ℃, roasting time 2～6 hours, adopt the method for flooding altogether or flooding respectively flooding active component nickel on the presintering carrier then, modifier and promoter, dip time is 0.5～6 hour, after the oven dry, under 400～600 ℃ temperature, decomposed 1～6 hour, and then repeated impregnations is decomposed once.

4. preparation method according to claim 3 is characterized in that described pore creating material is chosen as graphite, stearic acid, stearates, nitric acid, γ-Al ₂O ₃, cellulose or string, lubricant is chosen as graphite, stearic acid, stearates or nitric acid.

5. preparation method according to claim 4 is characterized in that described pore creating material is graphite or string, and lubricant is graphite or stearic acid.